Methods for altering the color and appearance of hair

ABSTRACT

Disclosed are methods and compositions for altering the color of hair, comprising treating the hair with a pre-alkalizing composition and then treating the hair with a color-altering composition comprising at least one direct dye and optionally at least one oxidative dye precursor.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationNo. 61/724,896, filed Nov. 9, 2012, which is incorporated herein byreference in its entirety.

BACKGROUND OF THE INVENTION

Chemical treatments on human hair, such as relaxers, straighteners,waves, perms, oxidative and direct dyes, highlights, lighteningcompositions and bleaches, are generally known to result in hairbreakage and loss, dryness, roughness and brittleness, and skin and/orscalp irritation. Such chemical treatments employ various reducing andoxidizing agents, alkalizing agents, and coloring agents that helpre-shape, artificially color, decolorize, modify the color shade/tone,or enhance the appearance and color of hair. Often times, these chemicaltreatments are used with the application of heat and mechanical combingor brushing, which may contribute to adversely affecting the conditionof the hair and the hair cuticle.

Thus, conventional and customary practice by consumers and hair dressersis to have a waiting period of at least 24 hours, preferably two weeks,in between two different chemical hair treatments in order to prevent orreduce irritation to the skin or scalp and the potential damage to haircaused by different chemical treatments within a short period of time,e.g., a few hours.

One example of the problems encountered with successively chemicallytreating the hair is that such chemical treatments may prevent thehair's color or shade from being lightened, bleached, dyed or alteredcorrectly after the chemical treatment, and therefore, prevent theconsumer from achieving the desired lightening or shade/color effects,especially when the lightening, bleaching, coloration or color-alteringstep is conducted immediately after the chemical treatment. Thus, awaiting period of at least 24 hours is generally recommended in order toreduce the chance of having a reaction between the different chemicaltreatments, for example, straightening then bleaching the hair, thatcould potentially result in an undesirable hair color or shade.

In order to address the concerns mentioned above, methods andcompositions have been proposed such as those that involve the use ofalternative ingredients and/or ingredients and compositions that areless harsh on hair and skin, including hair treatment regimens that mayminimize the problems arising from successive chemical treatments.However, there still exists a need to improve such methods andcompositions in order to formulate color-altering products and hairtreatment regimens or systems that allow the consumer to successivelychemically treat hair in a convenient and efficient manner, whicheffectively alter the color of and/or re-shape the hair while minimizingthe damage to the hair and other adverse effects to the consumer.

BRIEF SUMMARY OF THE INVENTION

The present disclosure is directed to methods and compositions foraltering the appearance of hair. Exemplary methods comprise applying apre-alkalizing composition to the hair, and subsequently applying acolor-altering composition to the hair. In at least certain exemplaryembodiments, the methods and compositions described allow for successivechemical treatments of the hair, while minimizing damage to the hairand/or skin (e.g. scalp).

By way of example, there is a need to provide methods and compositionsthat provide for hair to be chemically treated (e.g. straightened), andthen subsequently colored or lightened, while achieving a desired changein hair tone and minimizing damage to the hair. Lightening of the hairis typically evaluated by the tone height or level which describes thedegree or level of lightening. The notion of “tone” is based on theclassification of the natural shades, one tone separating each shadefrom the shade immediately following or preceding it, which is wellknown to hairstyling professionals. The tone heights or color levelsrange from 1 (black) to 10 (light blond), one unit corresponding to onetone; thus, the higher the number, the lighter the shade.

Accordingly, in various exemplary embodiments of the disclosure, themethods and compositions described allow one to achieve a desired levelof color or color “lift” in tone, i.e. to a higher number, whileminimizing damage to the hair and/or skin. In further exemplaryembodiments, the methods and compositions described below allow one todeposit color onto hair with no or minimal lift in the color.

Various exemplary methods according to the disclosure comprise:

-   -   (a) applying onto the hair, a pre-alkalizing composition having        a pH of from about 8 to about 14 to form pre-alkalized hair;    -   (b) optionally, rinsing the hair;    -   (c) applying a color-altering composition onto the pre-alkalized        hair, wherein the color-altering composition comprises, in a        cosmetically acceptable carrier,        -   (i) at least one direct dye; and        -   (ii) optionally at least one oxidative dye precursor;            -   and wherein the pH of the color-altering composition                ranges from about 1 to about 7;    -   (d) leaving the color-altering composition on the hair for a        time period sufficient to achieve a desired color; and    -   (e) optionally, rinsing the hair;    -   wherein the color-altering composition does not comprise a        chemical oxidizing agent; and    -   wherein the color-altering composition is applied onto the        pre-alkalized hair within about 24 hours after the        pre-alkalizing step.

Optionally, the color-altering composition additionally comprises atleast one additional ingredient chosen from fatty substances, de-dustingagents, alkoxyaminosilicones, silane compounds, ceramide compounds, andmetal catalyst compounds.

In further embodiments, methods for minimizing damage to the hair duringa process for altering the color of the hair are disclosed. Compositionsuseful for altering the appearance of the hair, and for minimizingdamage to the hair, are also disclosed.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory only,and are not restrictive of the invention as claimed. Other embodimentswill be apparent to those skilled in the art from consideration of thespecification and practice of the embodiments disclosed herein. It isintended that the specification and examples be considered as exemplaryonly, with the true scope and spirit of the invention being indicated bythe claims.

It is also to be understood that, while in various embodiments describedherein, steps of exemplary methods are recited in a particular order, itis intended that the disclosed steps may be carried out in any ordersuch that the properties intrinsically associated with the methods arenot, or are not substantially, adversely affected.

DETAILED DESCRIPTION

Exemplary embodiments of the disclosure comprise applying apre-alkalizing composition to the hair, and subsequently applying acolor-altering composition to the hair.

Pre-Alkalizing Composition

Various embodiments of the present invention provide for applying apre-alkalizing composition to the hair in a first step of the methodsdescribed herein. By first applying a pre-alkalizing composition to thehair, the hair is in a pre-alkalized form prior to further chemicaltreatments. Without wishing to be bound by theory, it is believed thatthe pre-alkalizing step opens the hair cuticle, thereby rendering itmore susceptible to penetration by the subsequently-applied composition.This in turn is believed to render the hair coloring, straightening,relaxing, etc., process more efficient and less time-consuming, whileminimizing damage.

The pre-alkalizing step may, for example, use an alkaline compositionhaving a pH ranging from about 8 to about 14, such as about 8 to about10.5, or about 8.5 to about 9.5. Acceptable alkaline compositions usefulherein are known in the art. By way of example, any conventional base,whether alkaline hydroxide or non-hydroxide, may be chosen as thepre-alkalizing composition, so long as it results in the formation of apre-alkalizing composition having the above-disclosed pH range. Theprecise amount of conventional base used will depend on the specificbase or bases chosen, which can be determined through routineexperimentation by those of ordinary skill in the art. Thepre-alkalizing composition may further comprise a cosmeticallyacceptable carrier.

The pre-alkalizing composition may be employed in any suitable form, solong as the hair, after application of the pre-alkalizing composition,has a pH that is alkaline. Examples include, but are not limited to, analkaline shampoo, an alkaline conditioner, or an alkaline solution ingeneral. In further exemplary embodiments, the pre-alkalizingcomposition may be a chemical treatment composition that is alkaline andthat causes a chemical reaction on the hair, such as, for example,relaxing, straightening, waving, perming, lightening the color, and/orpermanent, semi-permanent or demi-permanent coloring of the hair. In oneexemplary embodiment, the pre-alkalizing composition is in the form ofan alkaline shampoo which would facilitate both the pre-alkalizing andcleaning of the hair at the same time.

In various exemplary embodiments, the pre-alkalizing composition mayoptionally comprise at least one auxiliary ingredient. Exemplaryauxiliary ingredients useful in the pre-alkalizing composition accordingto various embodiments of the disclosure include, but are not limitedto, surfactants, rheology-modifying agents, chelants, fatty substances,ceramides, substantive polymers (cationic and/or amphoteric), ananhydrous and/or inert liquid, alkoxyaminosilicones, and silanes, aswell as other components typically used in cosmetic compositions, suchas, for example, fragrances.

The pre-alkalizing composition may be applied to the hair and remain incontact with the hair for a period of time sufficient to formpre-alkalized hair. For example, the pre-alkalizing composition may beleft on the hair for up to one hour, such as from about 5 minutes toabout 50 minutes, from about 10 minutes to about 40 minutes, or fromabout 15 minutes to about 30 minutes. In various exemplary embodiments,the pre-alkalizing composition may be left on the hair for up to about20 minutes, such as up to about 15 minutes, or up to about 10 minutes.

Once the hair has been pre-alkalized, the pre-alkalizing compositionmay, optionally, be rinsed off the hair before further chemicaltreatment is applied.

In various exemplary embodiments, after the hair has been pre-alkalized,and optionally the pre-alkalizing composition rinsed, the hair mayoptionally be shampooed and rinsed before further chemical treatment isapplied.

Color-Altering Composition

As a second step in various embodiments according to the disclosure, acolor-altering composition may be applied to the pre-alkalized hair. Thecolor-altering composition may, in at least certain embodiments, be in aready-to-use form.

The color-altering composition may, in various embodiments, be appliedonto the hair within about 24 hours, such as less than 24 hours or lessthan 12 hours, after the pre-alkalizing step. In at least certainexemplary embodiments, the color-altering composition may be applied tothe hair within a few hours (e.g. about 1 to about 6 hours) or a fewminutes (e.g. up to about 60 minutes) after the pre-alkalizing step.

According to various embodiments, the color-altering compositioncomprises, in a cosmetically acceptable carrier, at least one directdye.

As examples of synthetic direct dyes that are suitable for use, mentionmay be made of azo direct dyes, methine direct dyes, carbonyl directdyes, azine direct dyes, nitro (hetero) aryl direct dyes, especiallynitrobenzene dyes, and tri(hetero)arylmethane direct dyes, and theaddition salts thereof; alone or as mixtures.

For example, the azo dyes may comprise an —N═N— function in which thetwo nitrogen atoms are not simultaneously engaged in a ring. However, itis not excluded for one of the two nitrogen atoms of the sequence —N═N—to be engaged in a ring.

The dyes of the methine family are, by way of example, compoundscomprising at least one sequence chosen from >C═C< and —N═C< in whichthe two atoms are not simultaneously engaged in a ring. However, it ispointed out that one of the nitrogen or carbon atoms of the sequencesmay be engaged in a ring. More particularly, the dyes of this family arederived from compounds of true methine type (comprising one or moreabovementioned sequences —C═C—); of azomethine type (comprising at leastone, or more, sequences —C═N—) with, for example, azacarbocyanins andtheir isomers, diazacarbocyanins and their isomers, andtetraazacarbocyanins; of mono- and diarylmethane type; of indoamine (ordiphenylamine) type; of indophenol type; or of indoaniline type.

As regards the dyes of the carbonyl family, examples that may bementioned include dyes chosen from acridone, benzoquinone,anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone,pyrazol-anthrone, pyrimidinoanthrone, flavanthrone, idanthrone, flavone,(iso) violanthrone, isoindolinone, benzimid-azolone, isoquinolinone,anthrapyridone, pyrazolo-quinazolone, perinone, quinacridone,quinophthalone, indigoid, thioindigo, naphthalimide, anthrapyrimidine,diketopyrrolopyrrole and coumarin dyes.

As regards the dyes of the azine family, mention may be made, forexample, of azine, xanthene, thioxanthene, fluorindine, acridine,(di)oxazine, (di)thiazine and pyronin dyes.

The nitro (hetero) aromatic dyes are more particularly nitrobenzene ornitropyridine direct dyes.

As regards the dyes of porphyrin or phthalocyanin type, it is possibleto use cationic or non-cationic compounds, optionally comprising one ormore metals or metal ions, for instance alkali metals, alkaline-earthmetals, zinc and silicon. Examples of particularly suitable syntheticdirect dyes that may be mentioned include nitrobenzene dyes; azo directdyes; methine direct dyes; azomethine direct dyes, with, moreparticularly, diazacarbocyanins and isomers thereof andtetraazacarbocyanins (tetraazapentamethines); quinone direct dyes, andin particular anthraquinone, naphthoquinone or benzoquinone dyes; azinedirect dyes; xanthene direct dyes; triarylmethane direct dyes; indoaminedirect dyes; indigoid direct dyes; phthalocyanin and porphyrin directdyes; alone or as mixtures.

The direct dyes may be chosen from nitrobenzene dyes; azo dyes;azomethine dyes, with diazacarbocyanins and isomers thereof, andtetraazacarbocyanins (tetraazapentamethines); anthraquinone direct dyes;triarylmethane direct dyes; alone or as mixtures.

For example, these direct dyes may be chosen from nitrobenzene directdyes; azo direct dyes; azomethine direct dyes, with diazacarbocyaninsand isomers thereof, and tetraazacarbocyanins (tetraaza pentamethines);alone or as a mixture.

Among the nitrobenzene direct dyes that may be used, mention may be madein a non-limiting manner of the following compounds:1,4-diamino-2-nitrobenzene; I-amino-2-nitro-4-hydroxyethylaminobenzene;I-amino-2-nitro-4-bis(beta-hydroxyethyl)aminobenzene;1,4-bis(beta-hydroxyethylamino)-2-nitrobenzene;I-hydroxyethylamino-2-nitro-4-bis(beta-hydroxy-ethylamino)benzene;1-beta-hydroxyethyl amino-2-nitro-4-aminobenzene;I-hydroxyethylamino-2-nitro-4-(ethyl) (beta-hydroxy-ethyl)aminobenzene;I-amino-3-methyl-4-hydroxyethylamino-6-nitro-benzene;I-amino-2-nitro-4-hydroxyethylamino-5-chloro-benzene;1,2-diamino-4-nitrobenzene; I-amino-2-hydroxyethylamino-5-nitrobenzene;1,2-bis(beta-hydroxyethylamino)-4-nitrobenzene;I-amino-2-tris(hydroxymethyl)methyl-amino-5-nitro-benzene;I-hydroxy-2-amino-5-nitrobenzene; 1-hydroxy-2-amino-4-nitrobenzene;I-hydroxy-3-nitro-4-aminobenzene; I-hydroxy-2-amino-4,6-dinitrobenzene;I-hydroxyethyloxy-2-hydroxyethylamino-5-nitro-benzene;1-ethoxy-2-hydroxyethylamino-5-nitrobenzene;I-hydroxyethyloxy-3-methylamino-4-nitrobenzene; 1-beta,α-dihydroxypropyloxy-3-methylamino-4-nitro benzene;1-hydroxyethylamino-4, Y-dihydroxypropyloxy-2-nitrobenzene; 1-beta,Y-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene;1-beta-hydroxyethylamino-4-trifluoromethyl-2-nitro-benzene;1-beta-hydroxyethylamino-3-methyl-2-nitrobenzene;1-beta-aminoethylamino-5-methoxy-2-nitrobenzene;1-hydroxy-2-chloro-6-ethylamino-4-nitrobenzene;1-hydroxy-2-chloro-6-amino-4-nitrobenzene;1-hydroxy-6-bis(beta-hydroxyethyl)amino-3-nitro-benzene;α-beta-hydroxyethylamino-2-nitrobenzene; andI-hydroxy-4-beta-hydroxyethylamino-3-nitrobenzene.

Among the azo, azomethine, and methine direct dyes that may be usedaccording to the invention, mention may be made of the cationic dyesdescribed in patent applications WO 95/15144, WO 95/01772 and EP714954;FR2189006, FR2285851, FR2140205, EP1378544 and EP1674073, all of whichare incorporated by reference herein.

For example, the synthetic direct dyes may be chosen frommonochromophoric cationic direct dyes of the following types: azos;methines; azomethines with diazacarbocyanins and isomers thereof, andtetraazacarbocyanins; anthraquinones; alone or as a mixture.

Hence, mention may be made especially of the cationic direct dyescorresponding to the following formula (XVIII):

wherein, in formula (XVIII):

-   -   D represents a nitrogen atom or the —CH group,    -   R₁ and R₂, which may be identical or different, represent a        hydrogen atom; a C₁-C4 alkyl radical which may be substituted        with a —CN, —OH or —NH₂ radical, or form, with a carbon atom of        the benzene ring, an optionally oxygenous or nitrogenous        heterocycle that may be substituted with one or more C₁-C₄ alkyl        radicals; a 4′-aminophenyl radical,    -   R₃ and R′₃, which are identical or different, represent a        hydrogen or halogen atom chosen from chlorine, bromine, iodine        and fluorine, or a cyano, C₁-C₄ alkyl, C₁-C4 alkoxy or acetyloxy        radical,    -   X⁻ represents an anion chosen from chloride, methyl sulfate and        acetate,    -   A represents a group chosen from the following structures:

-   -   in which R₄ represents a C₁-C₄ alkyl radical that may be        substituted with a hydroxyl radical;

wherein:

-   -   R₅ represents a hydrogen atom, a C₁-C₄ alkoxy radical or a        halogen atom such as bromine, chlorine, iodine or fluorine, R₆        represents a hydrogen atom or a C₁-C₄ alkyl radical or forms,        with a carbon atom of the benzene ring, a heterocycle that is        optionally oxygenous and/or substituted with one or more C₁-C₄        alkyl groups,    -   R₇ represents a hydrogen or halogen atom such as bromine,        chlorine, iodine or fluorine,    -   D₁ and D₂ independently represent a nitrogen atom or the —CH        group,    -   m=0 or 1,    -   X⁻ represents a cosmetically acceptable anion that is chosen        from chloride, iodide, methyl sulfate, ethyl sulfate and        acetate,    -   E represents a group chosen from the following structures:

wherein:

-   -   R′ represents a C₁-C₄ alkyl radical; and    -   when m=0 and when D₁ represents a nitrogen atom, E may then also        denote a group of the following structure:

As other dyes that may be used according to the invention, mention mayalso be made, among the azo direct dyes, of the following dyes, whichare described in the Colour Index International, 3rd edition,incorporated by reference herein: Disperse Red 17; Disperse Red 13;Basic Red 22; Basic Red 76; Basic Yellow 57; Basic Brown 16; Basic Brown17; Disperse Green 9; Disperse Black 9; Solvent Black 3; Disperse Blue148; Disperse Violet 63; and Solvent Orange 7. Other azo dyes that maybe used according to the invention include Basic Red 46, Basic Violet35, and Disperse Orange 3.

Mention may also be made ofI-(4′-aminodiphenylazo)-2-methyl-4-bis(beta-hydroxyethyl)amino-benzene(INCI name: HC Yellow 7).

Among the quinone direct dyes that may be mentioned are the followingdyes: Disperse Red 15; Solvent Violet 13; Solvent Blue 14; DisperseViolet 1; Disperse Violet 4; Disperse Blue 1; Disperse Violet 8;Disperse Blue 3; Disperse Red 11; Disperse Blue 7; Disperse Blue 14;Basic Blue 22; Disperse Violet 15; Disperse Blue 377; Disperse Blue 60;Basic Blue 99; and also the following compounds:I-N-methylmorpholiniumpropylamino-4-hydroxyanthra-quinone;I-aminopropylamino-4-methylaminoanthraquinone;1-aminopropylamino-anthraquinone;5-beta-hydroxyethyl-1,4-diaminoanthraquinone;2-aminoethylaminoanthraquinone; and 1,4-bis(beta-dihydroxypropylamino)anthraquinone.

Mention may also be made of the coumarin compound Disperse Yellow 82.

Among the azine dyes that may be mentioned are the following compounds:Basic Blue 17; Basic Red 2; Solvent Orange 15.

Among the triarylmethane dyes that may be used according to theinvention, mention may be made of the following compounds: Basic Green1; Basic Violet 3; Basic Violet 14; Basic Blue 7; Basic Blue 26.

Among the indoamine dyes that may be used according to the invention,mention may be made of the following compounds:2-hydroxyethylamino-5-[bis(beta-4′-hydroxyethyl)amino]anilino-1,4-benzoquinone;2-hydroxyethylamino-5-(2′-methoxy-4′-amino)anilino-1,4-benzoquinone;3-N(2′-chloro-4′-hydroxy)phenylacetylamino-6-methoxy-1,4-benzoquinoneimine;3-N(3′-chloro-4′-methylamino)phenylureido-6-methyl-1,4-benzoquinoneimine;3-[4′-N-(ethylcarbamylmethyl)amino]phenylureido-6-methyl-1,4-benzoquinoneimine.

The cationic direct dyes may be, for example, chosen from direct dyes ofthe following types: azos, methines; azomethines, with diazacarbocyaninsand isomers thereof, and tetraazacarbocyanins (tetraazapentamethines);anthraquinones; alone or as a mixture.

For the nonionic dyes, compounds with a log P of greater than or equalto 2 may be chosen. As regards the synthetic direct dyes with a log P ofgreater than or equal to 2, it is known that the log P valueconventionally represents the partition coefficient of the dye betweenoctanol and water. The log P may be calculated according to the methoddescribed in the article by Meylan and Howard: Atom/Fragmentcontribution method for estimating octanol-water partition coefficients,J. Pharm. Sci., 84: 83-92, 1995, incorporated by reference herein. Thisvalue may also be calculated using numerous commercially availablesoftware packages, which determine the log P as a function of thestructure of a molecule. By way of example, mention may be made of theEpiwin software from the United States Environmental Agency.

For example, the dyes that are suitable for use in the invention arechosen from the following compounds, alone or as a mixture:

Dye Chemical structure log P

Disperse Red 17 3.69

Disperse Violet 1 3.0

HC Yellow 7 2.38

Disperse Blue 377 3.21

Disperse Red 13 5.22

Disperse Green 9 4.23

Solvent Black 3^(N) VJTV 7.50

Disperse Blue 148 4.81

Disperse Violet 63 5.30

Disperse Blue 60 3.38

OHN″″

Disperse Blue 14 4.25

OHN

Solvent Orange 15 3.90

Solvent Orange 7 4.40 O N—

Solvent Blue 14 8.18

OHN—

Disperse Yellow 82 3.68

For example, the direct dyes of the invention are chosen from cationicdyes of the following types: azos; methines; azomethines, withdiazacarbocyanins and isomers thereof, and tetraaza-carbocyanins(tetraazapentamethines); anthraquinones; alone or as a mixture, and inparticular dyes (AI) to (A6) mentioned previously, and also nonionicdyes with a log P of greater than or equal to 2.

Among the anionic direct dyes, mention may be made in particular ofthose described in the Colour Index International 3rd edition under thename Acid, and in particular: Disperse Red 17; Acid Yellow 9; Acid Black1; Acid Yellow 36; Acid Orange 7; Acid Red 33; Acid Red 35; Acid Yellow23; Acid Orange 24; Acid Violet 43; Acid Blue 62; Acid Blue 9; AcidViolet 49; and Acid Blue 7.

Exemplary direct dyes that may be used include those that are nonionic,anionic, and cationic. For example, the direct dye may be chosen fromnitrobenzene dyes, and acridine, acridone, anthranthrone,anthrapyrimidine, anthraquinone, azine, azo, azomethine, benzanthrone,benzimidazole, benzimidazolone, benzindole, benzoxazole, benzopyran,benzothiazole, benzoquinone, bis-azine, bis-isoindoline, carboxanilide,coumarin, cyanin (such as in particular azacarbocyanin,diazacarbocyanin, diazahemicyanin, hemicyanin, tetraazacarbocyanin),diazine, diketopyrrolopyrrole, dioxazine, diphenylamine,diphenylmethane, dithiazine, flavanthrone, flavone, fluorindine,formazan, hydrazone, hydroxy ketone, indamine, indanthrone, indigoid,indophenol, indoaniline, isoindoline, isoindolinone, isoviolanthrone,lactone, methine, naphthalimide, naphthanilide, naphtholactam,naphthoquinone, nitro, oxadiazole, oxazine, perilone, perinone,perylene, phenazine, phenothiazine, phthalocyanin, polyene/carotenoid,porphyrin, pyranthrone, pyrazolanthrone, pyrazolone, pyrimidinoanthrone,pyronine, quinacridone, quinoline, quinophthalone, squarane, stilbene,styryl, tetrazolium, thiazine, thioindigo, thiopyronine, triarylmethaneand xanthene dyes.

In various embodiments, direct dyes include, but are not limited to,cationic direct dyes, such as cationic mixed dyes including at least onechromophore, such as at least two chromophores, including thosedescribed in U.S. Pat. No. 7,172,633 and U.S. Pat. No. 7,582,122, bothof which are incorporated by reference herein. As used herein, “cationicmixed dye” means a dye whose cationic charge can form an integral partof the chromophore and/or of the linker, or alternatively a dye whosecationic charge is present via a substituent on the chromophore and/oron the linker. As used herein, “chromophore” means a radical derivedfrom a dye, i.e. a radical of a molecule that has at least oneabsorption maximum in the visible region between 400 and 800 nm, thisabsorbance requiring no prior oxidation or any combination with otherchemical species.

In various embodiments where the at least one dye is chosen from mixedcationic dyes, the at least one chromophore may be chosen from acridine,acridone, anthranthrone, anthrapyrimidine, anthraquinone, azine, azo,azomethine, benzanthrone, benzimidazole, benzimidazolone, benzindole,benzoxazole, benzopyran, benzothiazole, benzoquinone, bis-azine,bis-isoindoline, carboxanilide, coumarin, cyanins, diazine,diketopyrrolopyrrole, dioxazine, diphenylamine, diphenylmethane anddithiazine chromophores, flavonoids, fluorindines, formazans,hydrazones, hydroxy ketones, indamines, indanthrones, indigoids,pseudo-indigoids, indophenols, indoanilines, isoindolines, isoindolines,isoindolinones, isoviolanthrones, lactones, methines, naphthalimides,naphthanilides, naphtholactams, naphthoquinones, nitro dyes,oxadiazoles, oxazines, perilones, perinones, perylenes, phenazines,phenothiazines, phthalocyanin, polyenes/carotenoids, porphyrins,pyranthrones, pyrazolanthrones, pyrazolones, pyrimidinoanthrones,pyronines, quinacridones, quinolines, quinophthalones, squaranes,stilbenes, tetrazoliums, thiazines, thioindigo, thiopyronines,triarylmethanes, and xanthenes.

By way of example, cationic direct dyes may be chosen from compounds offormula (XIX):

wherein, in formula (XIX):

-   -   L is a linker chosen from cationic and non-cationic atoms or        groups of atoms separating the chromophores from the mixed dye,    -   R1 and R1′ are independently chosen from an alkyl radical, for        example C₁-C₆, optionally substituted with one or more hydroxyl,        C₁-C₂ alkoxy, C₂-C₄ (poly)hydroxyalkoxy, amino, C₁-C₂        (di)alkylamino or optionally substituted aryl radicals, and    -   R2 and R2′ are independently chosen from a C₁-C₆ alkyl radical,        optionally substituted with one or more hydroxyl, C₁-C₂ alkoxy,        C₂-C₄ (poly)hydroxyalkoxy, amino, C₁-C₂ (di)alkylamino radicals;        an optionally substituted phenyl radical; and    -   An represents one or more identical or different, monovalent or        multivalent anions.

By way of example, direct dyes of formula (XIII) that may be choseninclude the following:

In further embodiments, the at least one direct dye may be chosen fromdyes of formula (XX), such as those described in U.S. Pat. No.7,220,286, incorporated by reference herein:

wherein, in formula (XX):

-   -   W1 is chosen from —NR8- or —O—;    -   X1 represents N or CR9;    -   R1 and R2, independently, are chosen from a hydrocarbon chain;    -   R3 and R4, independently, are chosen from a hydrogen atom, a        halogen atom, a nitro group, a cyano group or a hydrocarbon        chain;    -   R5 to R9, independently, are chosen from a hydrogen atom or a        hydrocarbon chain; and    -   L represents one of the groups chosen from the following:

wherein:

-   -   R10 to R13, independently, are chosen from a hydrocarbon chain;    -   Y is chosen from a halogen atom, e.g. fluorine or chlorine;    -   the bond a is connected to the group W1 of formula (XX); and    -   X represents a cosmetically acceptable organic or mineral anion.

Direct dyes of formula (XX) also comprise a cosmetically acceptableanion that is organic or mineral in nature. By way of example of anionsthat are mineral in nature, mention may be made of halides, such aschlorides; hydroxides, sulphates; hydrogen sulphates. By way of examplesof anions that are organic in nature, suitable anions are, for instance,acetate; citrate; tartrate; alkyl sulphates for which the linear orbranched alkyl portion is a C₁-C₆ alkyl, such as the methosulphate orethosulphate ion; alkylsulphonates for which the linear or branchedalkyl portion is a C₁-C₆ alkyl; arylsulphonates for which the aryl, e.g.phenyl, portion is optionally substituted with one or more C₁-C₄ alkylradicals.

Exemplary direct dyes of formula (XX) include, but are not limited to:2-((E)-{4-[(3-{bis[3-({4-[(E)-(1,3-dimethyl-1H-imidazol-3-ium-2-yl)diazenyl]phenyl}amino)propyl]amino}propyl)amino]phenyl}diazenyl)-1,3-dimethyl-1H-imidazol-3-iumtrichloride2-{(E)-[4-({3-[bis[3-({4-[(E)-(1,3-dimethyl-1H-imidazol-3-ium-2-yl)diazenyl]phenyl}amino)propyl](methyl)ammonio]propyl}amino)phenyl]-diazenyl}-1,3-dimethyl-1H-imidazol-3-iumtetrachloride2-((E)-{4-[{3-[bis{3-[{4-[(E)-(1,3-dimethyl-1H-imidazol-3-ium-2-yl)diazenyl]phenyl}(methyl)amino]propyl}(methyl)ammonio]propyl}(methyl)amino]phenyl-}diazenyl)-1,3-dimethyl-1H-imidazol-3-iumtetrachloride2-((E)-{4-[{3-[bis{3-[{4-[(E)-(1,3-diethyl-1H-imidazol-3-ium-2-yl)diazenyl]phenyl}(ethyl)amino]propyl}(ethyl)ammonio]propyl}(ethyl)amino]phenyl}dia-zenyl)-1,3-diethyl-1H-imidazol-3-iumtetrachloride2-((E)-{4-[{3-[bis{3-[{4-((E)-(1,3-dimethyl-1H-imidazol-3-ium-2-yl)diazenyl]phenyl}(ethyl)amino]propyl}(ethyl)ammonio]propyl}(ethyl)amino]phenyl}di-azenyl)-1,3-dimethyl-1H-imidazol-3-iumtetrachloride2-((E)-{4-[(3-{3,5-bis[3-({4-[(E)-(1,3-dimethyl-1H-imidazol-3-ium-2-yl)diazenyl]phenyl}amino)propanoyl]-1,3,5-triazinan-1-yl}-3-oxopropyl]amino]phe-nyl}diazenyl)-1,3-dimethyl-1H-imidazol-3-iumtrichloride2-((E)-{4-[[3-(3,5-bis{3-[{4-[(E)-(1,3-dimethyl-1H-imidazol-3-ium-2-yl)di-azenyl]phenyl}(ethyl)amino]propanoyl}-1,3,5-triazinan-1-yl)-3-oxopropyl](ethyl)amino]phenyl}diazenyl)-1,3-dimethyl-1H-imidazol-3-iumtrichloride2-{(E)-[4-({2-[(3,5-bis{[2-({4-[(E)-(1,3-dimethyl-1H-imidazol-3-ium-2-yl)-diazenyl]phenyl}amino)ethyl]sulphonyl}-1,3,5-triazinan-1-yl)sulphonyl]ethy-l}amino)phenyl]diazenyl}-1,3-dimethyl-1H-imidazol-3-iumtrichloride2-((E)-{4-[(2-{[3,5-bis({2-[{4-[(E)-(1,3-dimethyl-1H-imidazol-3-ium-2-yl)-diazenyl]phenyl}(ethyl)amino]ethyl}sulphonyl)-1,3,5-triazinan-1-yl]sulphon-yl}ethyl)(ethyl)amino]phenyl}diazenyl)-1,3-dimethyl-1H-imidazol-3-iumtrichloride2-[(E)-(4-{[4,6-bis({4-[(E)-(1,3-dimethyl-1H-imidazol-3-ium-2-yl)diazenyl-]phenyl}amino)-1,3,5-triazin-2-yl]amino}phenyl)diazenyl]-1,3-dimethyl-1H-i-midazol-3-iumtrichloride2-((E)-{4-[{4,6-bis[{4-[(E)-(1,3-dimethyl-1H-imidazol-3-ium-2-yl)diazenyl-]phenyl}(methyl)amino]-1,3,5-triazin-2-yl}(methyl)amino]phenyl}diazenyl)-1-,3-dimethyl-1H-imidazol-3-iumtrichloride 2-[(E)-(4-{[5Chloro-2,6-bis({4-[(E)-(1,3-dimethyl-1H-imidazol-3-ium-2-yl)diazenyl]phen-yl}amino)pyrimidin-4-yl]amino}phenyl)diazenyl]-1,3-dimethyl-1H-imidazol-3-iumtrichloride 2-((E)-{4-[{5Chloro-2,6-bis[{4-[(E)-(1,3-dimethyl-1H-imidazol-3-ium-2-yl)diazenyl]phenyl}(methyl)amino]pyrimidin-4-yl}(methyl)amino]-phenyl}diazenyl)-1,3-dimeth-yl-1H-imidazol-3-iumtrichloride.

In various exemplary embodiments, the at least one direct dye is chosenfrom hydroxyethyl-2-nitro-p-toluidine and3-methylamino-4-nitrophenoxyethanol.

In various embodiments, the at least one direct dye may be present in anamount ranging from about 0.001% to about 20% by weight, such as fromabout 0.005% to about 10% by weight, or from about 0.01% to about 5% byweight, based on the total weight of the color-altering composition.

The color-altering composition may optionally comprise at least onechemical oxidizing agent chosen from peroxides, persulfates, perborates,percarbonates, peracids, bromates, their salts and mixtures thereof. Theat least one chemical oxidizing agent may, optionally, be water-soluble.

Optional peroxides useful herein include, for example, hydrogenperoxide, magnesium peroxide, PVP-peroxide, calcium peroxide, and sodiumperoxide. In other embodiments, the color-altering composition does notcomprise a chemical oxidizing agent. In such cases, the composition maybe optionally oxidized by environmental circumstances, e.g., air mayserve as the oxidizing agent.

According to one embodiment, the color-altering composition does notcontain any, or contains substantially no, peroxide, such as hydrogenperoxide (H2O2). Peroxides, such as hydrogen peroxide, are known in theart as potentially damaging to the hair fibers, particularly when leftin contact with the fibers for extended periods of time during dyeingprocesses. It would therefore be advantageous to provide a dyeingprocess that does not employ peroxides, for instance, a dyeing processwherein the color-altering composition does not comprise peroxides, suchas hydrogen peroxide.

Exemplary, non-limiting persulfates include potassium persulfate, sodiumpersulfate, and ammonium persulfate. In various embodiments, exemplaryoxidizing agents may be chosen from sodium perborate and sodiumpercarbonate. In further embodiments, exemplary peracids may be chosenfrom organic peracids having the general formula (I):

R—C(O)OOH

wherein, in formula (I), R is chosen from saturated or unsaturated,substituted or unsubstituted, straight or branched chain, alkyl, aryl oralkaryl groups having from 1 to 22 carbon atoms. In at least someexemplary embodiments, mixtures of two or more oxidizing agents chosenfrom persulfates, perborates, percarbonates, peracids, bromates, andsalts thereof, may be chosen.

In various embodiments, the at least one chemical oxidizing agent ischosen from alkali metal salts of perborates, percarbonates, bromates,and persulfates, such as, for example, ammonium, sodium, and potassiumsalts. In further embodiments, the color-altering composition comprisessubstantially no chemical oxidizing agent, and in yet furtherembodiments, the color-altering composition does not comprise a chemicaloxidizing agent.

The color-altering composition may optionally further comprise at leastone oxidative dye precursor. Useful oxidative dye precursors include, byway of example only, aromatic diamines, polyhydric phenols, aminophenols, and derivatives of these compounds, such as, for example,N-substituted derivatives of the amines, and ethers of the phenols.

By way of non-limiting example, oxidative dye precursors may be chosenfrom ortho- or para-aminophenols, ortho- or para-phenylenediamines,double bases, heterocyclic bases, and the acid addition salts thereof.

Exemplary para-phenylenediamines which may be chosen include compoundsof the general formula (XXIII) and their addition salts with an acid:

wherein, in formula (XXIII):

-   -   R8 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4        monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a        (C1-C4)alkoxy(C1-C4)alkyl radical, a C1-C4 alkyl radical        substituted by a nitrogenous group, a phenyl radical or a        4′-aminophenyl radical;    -   R9 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4        monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a        (C1-C4)alkoxy(C1-C4)alkyl radical or a C1-C4 radical substituted        by a nitrogenous group;    -   R8 and R9 can also form, with the nitrogen atom which carries        them, a 5- or 6-membered nitrogenous heterocycle optionally        substituted by one or more alkyl, hydroxyl or ureido groups;    -   R10 represents a hydrogen atom, a halogen atom, such as a        chlorine atom, a C1-C4 alkyl radical, a sulpho radical, a        carboxyl radical, a C1-C4 monohydroxyalkyl radical, a C1-C4        hydroxyalkoxy radical, a C1-C4 acetylaminoalkoxy radical, a        C1-C4 mesylaminoalkoxy radical or C1-C4 carbamoylaminoalkoxy        radicals; and    -   R11 represents a hydrogen atom, a halogen atom or a C1-C4 alkyl        radical.

By way of example, among the nitrogenous groups in the above formula(XXIII), of the amino, mono(C1-C4)alkylamino, di(C1-C4)alkylamino,tri(C1-C4)alkylamino, monohydroxy(C1-C4)alkylamino, imidazolinium andammonium radicals may be chosen. Exemplary para-phenylenediamines ofabove formula (XXIII), include para-phenylenediamine,para-toluylenediamine, 2-chloro-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine,2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine,N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine,N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline,N,N-bis(beta-hydroxyethyl)-para-phenylenediamine,4-N,N-bis(beta-hydroxyethyl)amino-2-methylaniline,4-N,N-bis(beta-hydroxyethyl)amino-2-chloroaniline,2-(beta-hydroxyethyl)-para-phenylenediamine,2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine,N-(beta-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-beta-methyl-para-phenylenediamine,N-ethyl-N-(beta-hydroxyethyl)-para-phenylenediamine,N-(beta,gamma-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine,2-((beta-hydroxyethyloxy)-para-phenylenediamine,2-((beta-acetylaminoethyloxy)-para-phenylenediamine,N-(beta-methoxyethyl)-para-phenylenediamine,2-methyl-1-N-(beta-hydroxyethyl)-para-phenylenediamine and theiraddition salts with an acid.

Exemplary ortho-phenylenediamines, includeN1-(2-hydroxyethyl)-4-nitro-o-phenylenediamine,4-methyl-o-phenylenediamine, and 4-nitro-o-phenylenediamine and acidaddition salts thereof.

As used herein, the term “double bases” means compounds comprising atleast two aromatic nuclei having at least one of amino and hydroxylgroups. For example, double bases may be chosen from compounds of theformula (XXIV) and their addition salts with an acid:

wherein, in formula (XXIV):

-   -   Z1 and Z2 may independently be chosen from a hydroxyl or —NH2        radical which can be substituted by a C1-C4 alkyl radical or by        a connecting arm Y;    -   the connecting arm Y is chosen from a linear or branched        alkylene chain comprising from 1 to 14 carbon atoms which can be        interrupted or terminated by one or more nitrogenous groups        and/or by one or more heteroatoms, such as oxygen, sulphur or        nitrogen atoms, and which is optionally substituted by one or        more hydroxyl or C1-C6 alkoxy radicals;    -   R12 and R13 are independently chosen from a hydrogen or halogen        atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a        C2-C4 polyhydroxyalkyl radical, a C1-C4 aminoalkyl radical or a        connecting arm Y;    -   R14, R15, R16, R17, R18 and R19 are independently chosen from a        hydrogen atom, a connecting arm Y or a C1-C4 alkyl radical;        wherein compounds of formula (XXIV) only comprise a single        connecting arm Y per molecule.

In various embodiments, nitrogenous groups of the above formula (XXIV),may be chosen from amino, mono(C1-C4)alkylamino, di(C1-C4)alkylamino,tri(C1-C4)alkylamino, monohydroxy(C1-C4)alkylamino, imidazolinium andammonium radicals.

Nonlimiting examples of double bases includeN,N′-bis(beta-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diamino-propan-ol,N,N′-bis(beta-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(beta-aminophenyl)-tetramethylenediamine,N,N′-bis(4-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-diethyl-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine,1,8-bis(2,5-diamino-phenoxy)-3,5-dioxaoctane, and their addition saltswith an acid.

Non-limiting examples of para-aminophenols which can be used in thecontext of the invention can be chosen in particular from the compoundscorresponding to the following formula (XXV): and their addition saltswith an acid:

wherein, in formula (XXV):

-   -   R20 is chosen from a hydrogen atom, a halogen atom, such as        fluorine, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl        radical, a (C1-C4)alkoxy(C1-C4)alkyl radical, a C1-C4 aminoalkyl        radical or a hydroxy(C1-C4)alkylamino-(C1-C4)alkyl radical, and    -   R21 is chosen from a hydrogen atom, a halogen atom, such as        fluorine, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl        radical, a C2-C4 polyhydroxyalkyl radical, a C1-C4 aminoalkyl        radical, a C1-C4 cyanoalkyl radical or a (C1-C4) alkoxy(C1-C4)        alkyl radical.

By way of example only, para-aminophenol, 4-amino-3-methylphenol,4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethyl phenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(beta-hydroxyethylaminomethyl)phenol,N-methyl-para-aminophenol, and the acid addition salts thereof may bechosen.

Exemplary ortho-aminophenols may be chosen from 2-aminophenol,2-amino-1-hydroxy-5-methylbenzene, 2-amino-1-hydroxy-6-methylbenzene,5-acetamido-2-aminophenol, and the acid addition salts thereof.

Exemplary heterocyclic bases may be chosen from pyridine derivatives,pyrimidine derivatives, pyrazole derivatives, pyrazolinone derivatives,and the acid addition salts thereof.

Non-limiting examples of pyridine derivatives include, for example,those disclosed in GB1026978 and GB1153196, both incorporated byreference herein, such as 2,5-diaminopyridine,2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine,2-(beta-methoxyethyl)amino-3-amino-6 methoxypyridine,3,4-diaminopyridine, and the acid addition salts thereof.

Non-limiting examples of pyrimidine derivatives include, for example,those described in DE 2 359 399, JP 88-169 571, JP 91-10659 and WO96/15765, all incorporated by reference herein, such as2,4,5,6-tetra-aminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,2-hydroxy-4,5,6-triamino-pyrimidine,2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and thepyrazolopyrimidine derivatives, such as those mentioned in FrenchApplication FR-A-2 750 048 and among which may be mentionedpyrazolo[1,5-a]pyrimidine-3,7-diamine;2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;pyrazolo[1,5-a]pyrimidine-3,5-diamine;2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine;3-aminopyrazolo[1,5-a]pyrimidin-7-ol;3-aminopyrazolo[1,5-a]pyrimidin-5-ol;2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol;2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol;2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)(2-hydroxyethyl)aminolethanol;2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)(2-hydroxyethyl)amino]ethanol;5,6-dimethyl-pyrazolo[1,5-a]pyrimidine-3,7-diamine;2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;3-amino-5-methyl-7-(imidazolylpropylamino)pyrazolo[1,5-a]pyrimidine; andtheir addition salts and their tautomeric forms, when there exists atautomeric equilibrium, and their addition salts with an acid.

Non-limiting examples of pyrazole and pyrazolinone derivatives includethe compounds described in DE 3,843,892, DE 4,133,957, WO 94/08969, WO94/08970, FR-A-2,733,749, and DE 195 43 988, all of which areincorporated by reference herein, such as 4,5-diamino-1-methyl-pyrazole,3,4-diaminopyrazole, 4,5-diamino-1-(4′-chlorobenzyl)pyrazole,4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole,4,5-diamino-1-methyl-3-phenylpyrazole,4-amino-1,3-dimethyl-5-hydrazinopyrazole,1-benzyl-4,5-diamino-3-methylpyrazole,4,5-diamino-3-tert-butyl-1-methylpyrazole,4,5-diamino-1-tert-butyl-3-methylpyrazole,4,5-diamino-1-(beta-hydroxyethyl)-3-methylpyrazole,4,5-diamino-1-(beta-hydroxyethyl)pyrazole,4,5-diamino-1-ethyl-3-methylpyrazole,4,5-diamino-1-ethyl-3-(4′-methoxyphenyl) pyrazole,4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,4,5-diamino-3-hydroxymethyl-1-methylpyrazole,4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,4,5-diamino-3-methyl-1-isopropylpyrazole,4-amino-5-(2′-aminoethyl)amino-1,3-dimethyl-pyrazole,3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole,3,5-diamino-1-methyl-4-methylaminopyrazole,3,5-diamino-4-(p-hydroxyethyl)amino-1-methylpyrazole,2-(4,5-diamino-1H-pyrazol-1-yl), H₂SO₄,2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-z]pyrazol-1-one,1-methyl-3-phenyl-2-pyrazolinone, and the acid addition salts thereof.

The at least one oxidation dye precursor may be present in an amountranging from, for example, about 0.0001% to about 12%, such as fromabout 0.0001% to about 8.0%, or from about 0.005% to about 5% by weight,based on the total weight of the composition.

The color-altering composition may optionally further comprise at leastone lift-enhancing agent. Lift-enhancing agents that may be useful inthe color-altering composition include those that are capable ofgenerating ammonia. By way of example only, lift-enhancing agents may bechosen from ammonium salts, amino acids, and urea and derivativesthereof.

Exemplary ammonium salts may be chosen from ammonium chloride, ammoniumsulphate, ammonium nitrate, ammonium phosphate, ammonium acetate,ammonium carbonate, ammonium hydrogen carbonate, ammonium carbamate, andmixtures thereof.

Quaternary ammonium or diammonium salts may optionally be used. By wayof example only, those described in US2005071933, incorporated byreference herein, may be chosen, such as, for example, those of thegeneral formula (XXI):

wherein, in formula (XXI):

-   -   R1 and R4, may independently be chosen from saturated or        unsaturated, linear or branched, aliphatic hydrocarbon radicals        comprising from 1 to about 30 carbon atoms, or an alkoxy,        alkoxycarbonylalkyl, polyoxyalkylene, alkylamido,        alkylamidoalkyl, hydroxyalkyl, aromatic, aryl or alkylaryl        radical comprising from about 12 to about 30 carbon atoms, with        at least one radical among R1, R2, R3 and R4 denoting a radical        comprising from 8 to 30 carbon atoms; and —X⁻ is an anion chosen        from the group comprising halides, phosphates, acetates,        lactates and alkyl sulphates;

and/or general formula (XXII):

wherein, in formula (XXII):

-   -   R6 denotes an aliphatic radical comprising from about 16 to 30        carbon atoms,    -   R7, R8, R9, R10 and R11 are independently chosen from hydrogen        or an alkyl radical comprising from 1 to 4 carbon atoms, and    -   X⁻ is an anion chosen from the group comprising halides,        acetates, phosphates and sulphates.

Quaternary ammonium and diammonium salts include, for example,distearyldimethylammonium chloride, cetyltrimethylammonium chloride,behenyltrimethylammonium chloride, oleocetyldimethylhydroxyethylammoniumchloride, stearamidopropyldimethyl (myristyl acetate) ammonium chloride,di(C₁-C₂ alkyl)(C₁₂-C₂₂ alkyl)hydroxy(C₁-C₂alkyl)ammonium salt, such asdialkyldimethylammonium or alkyltrimethylammonium salt in which thealkyl radical comprises 12 to 22 carbon atoms, andpropanetallowdiammonium dichloride.

Imidazolium salts may also be used, such as, for example, the productsold as REWOQUAT W 7500 by the company REWO.

As examples of amino acids that may be chosen, mention may be made ofaspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline,asparagine, carnitine, cysteine, glutamine, glycine, histidine, lysine,isoleucine, leucine, methionine, N-phenylalanine, proline, serine,taurine, threonine, tryptophan, tyrosine and valine.

In various embodiments, the at least one lift-enhancing agent may bepresent in an amount ranging from about 0.01% to about 10% by weight,such as from about 0.05% to about 5% by weight, based on the totalweight of the composition.

The color-altering composition may also comprise a cosmeticallyacceptable carrier. The cosmetically acceptable carrier may, forexample, be present in the color-altering composition in an amountranging from about 1% to about 40% by weight, such as from about 5% toabout 35% by weight, or about 10% to about 30% by weight of thecolor-altering composition.

Auxiliary ingredients may be added to the color-altering composition.Exemplary auxiliary ingredients useful in the color-altering compositionaccording to various embodiments of the disclosure include, but are notlimited to, rheology-modifying agents, activators, chelants, fattysubstances, ceramides, alkoxyaminosilicones, and silanes, andlift-enhancing agents chosen from metal catalyst compounds.

The color-altering composition may also contain acid and alkali pHadjusters, which are well known in the art in the cosmetic treatment ofkeratin fibers, such as hair. Such pH adjusters include, but are notlimited to, sodium metasilicate, silicate compounds, citric acid,ascorbic acid, and carbonate compounds.

The pH adjusters may, in various embodiments, be present in thecolor-altering composition in an amount effective to provide thecolor-altering composition with a pH of not greater than 7, such as a pHranging from about 1 to about 7, from about 2 to about 6, or from about3 to about 5. By way of example, the amount of pH adjuster may bepresent, in various embodiments, in an amount of at least about 0.01%,such as at least about 0.1%, at least about 0.2%, or at least about0.5%.

The color-altering composition may be left on the hair for a period oftime sufficient to achieve the desired alteration in hair tone/color.For example, the color-altering composition may be left on the hair forup to one hour, such as from about 3 minutes to about 45 minutes, fromabout 5 minutes to about 30 minutes, or from about 10 minutes to about20 minutes. In further embodiments, the color-altering composition maybe left on the hair for a period up to about 30 minutes, such as, forexample, from about 1 to about 30 minutes, about 1 to about 10 minutes,or about 1 to about 5 minutes. One skilled in the art will, byconsidering various factors such as the starting and desired color ofthe hair, be able to determine an appropriate amount of time to leavethe color-altering composition on the hair in order to achieve thedesired alternation in hair color.

If desired, the color-altering composition may, optionally, be rinsedoff the hair.

Post-Treatment Composition

Optionally, in at least some exemplary embodiments, a post-treatmentcomposition may be applied to the hair. The post-treatment step may beperformed at any time subsequent to the pre-alkalizing andcolor-altering steps.

The post-treatment composition may be any composition for treating hair,and may include, for example, a conditioning composition, a permanentwaving composition, a straightening composition, and/or a compositionfor coloring the hair. The post-treatment composition may be in anyform, such as, for example, the form of a shampoo, a rinse conditioner,a non-rinse conditioner, or a leave-on treatment composition.

In at least one exemplary embodiment, the post-treatment composition maybe chosen from a surfactant-based composition. The surfactant-basedcomposition may contain at least one surfactant chosen from anionic,amphoteric, non-ionic, zwitterionic, and cationic surfactants, andmixtures thereof. The exemplary surfactant-based composition may alsocomprise a cosmetically acceptable carrier.

The at least one surfactant in the surfactant-based composition may bepresent in an amount ranging from about 0.01% to about 40%, such as fromabout 0.05% to about 30%, relative to the total weight of thesurfactant-based composition.

In various exemplary embodiments, the post-treatment composition mayoptionally further comprise at least one auxiliary ingredient. Exemplaryauxiliary ingredients that may be useful in the post-treatmentcomposition according to various embodiments of the disclosure include,but are not limited to, rheology-modifying agents, chelants, fattysubstances, ceramides, alkoxyaminosilicones, and silanes.

Cosmetically Acceptable Carrier

Cosmetically acceptable carriers useful according to various embodimentsdescribed herein may, by way of non-limiting example, be chosen fromwater, organic solvents, natural oils, synthetic oils, esters,hydrocarbons, silicones, and mixtures thereof. Non-limiting examples ofcosmetically acceptable carriers include alcohols, such as ethanol,isopropyl alcohol, benzyl alcohol and phenyl ethyl alcohol; glycols andglycol ethers, such as propylene glycol, hexylene glycol, ethyleneglycol monomethyl, monoethyl or monobutyl ether, propylene glycol andits ethers, such as propylene glycol monomethyl ether, butylene glycol,dipropylene glycol, and also diethylene glycol alkyl ethers, such asdiethylene glycol monoethyl ether and monobutyl ether; hydrocarbons suchas straight chain hydrocarbons, mineral oil, polybutene, hydrogenatedpolyisobutene, hydrogenated polydecene, polydecene, squalene, petrolatumand isoparaffins; and mixtures thereof, to name a few.

Auxiliary Ingredients

The pre-alkalizing composition, the color-altering composition, and/orthe post-treatment composition may, optionally, comprise one or moreauxiliary ingredients chosen from rheology-modifying agents, activators,direct dyes, chelants, fatty substances, ceramides,alkoxyaminosilicones, silanes, and lift-enhancing agents, such asnitrogen-containing compounds and metal catalyst compounds. It is to beunderstood that various compounds can serve more than one intendedpurpose. For example, amino acids such as glycine may act as both alift-enhancing agent and an activator.

Rheology-Modifying Agents

Exemplary rheology-modifying agents that may be used according to thedisclosure include, but are not limited to, nonionic, anionic, cationic,or amphoteric polymers, and other rheology modifiers such ascellulose-based thickeners (e.g. hydroxyethylcellulose,hydroxypropylcellulose, carboxymethylcellulose, cationic cellulose etherderivatives, quaternized cellulose derivatives, etc.), guar gum and itsderivatives (e.g. hydroxypropyl guar, cationic guar derivatives, etc.),gums of microbial origin (e.g. xanthan gum, scleroglucan gum, etc.),crosslinked homopolymers of acrylic acid or ofacrylamidopropane-sulfonic acid, associative polymers, non-associativethickening polymers, and water-soluble thickening polymers, as describedbelow.

In various exemplary embodiments, the compositions according to thedisclosure may comprise at least one polymer chosen from nonionic,anionic, cationic or amphoteric amphiphilic polymers.

The amphiphilic polymers may, optionally, contain a hydrophobic chainthat is a saturated or unsaturated, aromatic or non-aromatic, linear orbranched C₆-C₃₀ hydrocarbon-based chain, optionally comprising one ormore oxyalkylene (oxyethylene and/or oxypropylene) units.

Exemplary, non-limiting cationic amphiphilic polymers comprising ahydrophobic chain that may be chosen are cationic polyurethanes orcationic copolymers comprising vinyllactam units, such asvinylpyrrolidone units.

As non-limiting examples of nonionic amphiphilic polymers containing ahydrophobic chain, mention may be made, inter alia, of:

(1) celluloses modified with groups comprising at least one saturated orunsaturated, linear or branched C₆-C₃₀ hydrocarbon-based chain, forinstance hydroxyethylcelluloses modified with groups comprising at leastone hydrophobic chain as defined previously, such as especially NatrosolPlus Grade 330 CS (C₁₆ alkyls—sold by the company Aqualon); BermocollEHM 100 (sold by the company Berol Nobel), Amercell Polymer HM-1500(hydroxyethylcellulose modified with a polyethylene glycol (15)nonylphenyl ether group-sold by the company Amerchol);

(2) hydroxypropyl guars modified with groups comprising at least onehydrophobic chain as defined, for example Jaguar XC-95/3 (C₁₄ alkylchain-sold by the company Rhodia Chimie); Esaflor HM 22 (C₂₂ alkylchain-sold by the company Lamberti); RE210-18 (C₁₄ alkyl chain) andRE205-1 (C₂₀ alkyl chain-sold by the company Rhodia Chimie);

(3) copolymers of vinylpyrrolidone and of hydrophobic monomerscontaining a hydrophobic chain as defined above, for instance Antaron orGanex V216 (vinylpyrrolidone/hexadecene copolymers); Antaron or GanexV220 (vinylpyrrolidone/eicosene copolymers), sold by the company I.S.P.;

(4) copolymers of C₁-C₆ alkyl(meth)acrylates and of amphiphilic monomerscontaining a hydrophobic chain;

(5) copolymers of hydrophilic (meth)acrylates and of hydrophobicmonomers comprising at least one hydrophobic chain, for instance thepolyethylene glycol methacrylate/lauryl methacrylate copolymer;

(6) polymers with an aminoplast ether skeleton containing at least onefatty chain, such as the Pure Thix compounds sold by the companySud-Chemie;

(7) linear (block structure), grafted, or starburst polyurethanepolyethers comprising in their chain at least one hydrophilic block,which is generally a polyoxyethylene block which may comprise between 50and 1000 oxyethylene units approximately, and at least one hydrophobicblock, which may comprise aliphatic groups alone, optionally combinedwith cycloaliphatic and/or aromatic blocks. In various embodiments, thepolyurethane polyethers comprise at least two C₆-C₃₀ hydrocarbon-basedhydrophobic chains, separated by a hydrophilic block; the hydrophobicchains may be pendent chains or chains with one or more of the endgroups of the hydrophilic block(s).

The polyurethane polyethers may comprise a urethane bond between thehydrophilic blocks, but may also contain hydrophilic blocks linked tothe lipophilic blocks via other chemical bonds. Examples of polyurethanepolyethers that may be used include, but are not limited to, Nuvis FX1100 (European and US INCI name “Steareth-100/PEG-136/HMDI Copolymer”sold by the company Elementis Specialties); Rheolate® 205, 208, 204 or212 (sold by the company Rheox) and also Acrysol RM 184® (sold by thecompany Rohm & Haas); Elfacos T210® (C₁₂-C₁₄ alkyl chain) and ElfacosT212® (C₁₈ alkyl chain) sold by the company Akzo. The product DW 1206B®from Rohm and Haas comprising a C₂₀ alkyl chain and comprising aurethane bond, provided at a solids content of 20 percent in water, canalso be used.

Use may also be made of solutions or dispersions of these polymers, forexample in water or in an aqueous/alcoholic medium, such as polymers ofRheolate® 255, Rheolate® 278 and Rheolate® 244, sold by Rheox, and DW1206F and DW 1206J provided by Rohm and Haas.

The anionic amphiphilic polymers containing a hydrophobic chain that maybe used may comprise, as hydrophobic chain, at least one saturated orunsaturated, aromatic or non-aromatic, linear or branched C₈-C₃₀hydrocarbon-based chain.

More particularly, the anionic amphiphilic polymers comprising at leastone hydrophobic chain which are crosslinked or non-crosslinked, compriseat least one hydrophilic unit derived from one or more ethylenicallyunsaturated monomers bearing a carboxylic acid function, or a sulphonicfunction which is free or partially or totally neutralized, and at leastone hydrophobic unit derived from one or more ethylenically unsaturatedmonomers bearing a hydrophobic side chain, and optionally at least onecrosslinking unit derived from one or more polyunsaturated monomers.

The amphiphilic polymers may also optionally comprise at least onesulphonic group, in free or partially- or totally-neutralized form, andat least one hydrophobic portion.

Among these, mention may be made, by way of example, ofacrylamido-2-methyl-2-propanesulphonic (AMPS) acid/n-dodecylacrylamidecopolymer neutralized with sodium hydroxide, the copolymer crosslinkedwith methylenebisacrylamide consisting of 75% by weight of AMPS unitsneutralized by NH₃ and 25% by weight of Genapol® T-250 acrylate units,the copolymer crosslinked with allyl methacrylate consisting of 90% byweight of AMPS units neutralized with NH₃ and 10% by weight of Genapol®T-250 methacrylate units, or the copolymer crosslinked with allylmethacrylate consisting of 80% by weight of AMPS units neutralized withNH₃ and 20% by weight of Genapol® T-250 methacrylate units.

Other non-limiting examples include Carbopol® ETD-2020 (acrylicacid/C₁₀-C₃₀ alkyl methacrylate crosslinked copolymer sold by thecompany Noveon); Carbopol® 1382, Pemulen TR1 and Pemulen TR2 (acrylicacid/C₁₀-C₃₀ alkyl acrylate crosslinked copolymers-sold by the companyNoveon), the methacrylic acid/ethyl acrylate/oxyethylenated stearylmethacrylate copolymer (55/35/10); the (meth)acrylic acid/ethylacrylate/25 EO oxyethylenated behenyl methacrylate copolymer (ACULYN® 28sold by Rohm & Haas) and the methacrylic acid/ethyl acrylate/steareth-10allyl ether crosslinked copolymer.

Other suitable examples include anionic thickening polymers chosen fromcrosslinked terpolymers of methacrylic acid, ethyl acrylate, andpolyethylene glycol (10 EO) stearyl alcohol ether (Steareth 10), such asthe products sold by the company ALLIED COLLOIDS under the namesSALCARE® SC 80 and SALCARE® SC 90, which are aqueous emulsionscomprising 30% of a crosslinked terpolymer of methacrylic acid, of ethylacrylate and of steareth-10-allyl ether (40/50/10).

Anionic thickening polymers comprising at least one fatty chain can alsobe chosen from: (1) terpolymers formed from maleic anhydride/C₃₀-C₃₈alpha-olefin/alkyl maleate such as the product (maleic anhydride/C₃₀-C₃₈alpha-olefin/isopropyl maleate copolymer) sold under the name PERFORMA®1608 by the company NEWPHASE TECHNOLOGIES™, (2) acrylic terpolymersformed from: (a) 20% to 70% by weight of a carboxylic acid withα,β-monoethylenic unsaturation; (b) 20% to 80% by weight of anonsurfactant monomer with α,β-monoethylenic unsaturation different from(a); (c) 0.5% to 60% by weight of a nonionic monourethane which is theproduct of the reaction of a monohydric surfactant with a monoisocyanatewith monoethylenic unsaturation, (3) copolymers formed from at least twomonomers, wherein at least one of said at least two monomers is chosenfrom a carboxylic acid with α,β-monoethylenic unsaturation, an ester ofa carboxylic acid with α,β-monoethylenic unsaturation, and anoxyalkylenated fatty alcohol; and (4) copolymers formed from at leastthree monomers, wherein at least one of said at least three monomers ischosen from a carboxylic acid with α,β-monoethylenic unsaturation, atleast one of said at least three monomers is chosen from an ester of acarboxylic acid with α,β-monoethylenic unsaturation and at least one ofsaid at least three monomers is chosen from an oxyalkylenated fattyalcohol.

Additionally, these compounds can also comprise, as monomer, acarboxylic acid ester comprising an α,β-monoethylenic unsaturation and aC₁-C₄ alcohol. By way of example of this type of compound, there may bementioned ACULYN® 22 sold by the company ROHM and HAAS, which is anoxyalkylenated stearyl methacrylate/ethyl acrylate/methacrylic acidterpolymer.

When the compositions according to various embodiments of the disclosurecomprise one or more amphiphilic polymer(s) containing a hydrophobicchain, then this or these polymer(s) generally represent(s) from about0.01% to about 20% by weight, such as, for example, from about 0.05% toabout 10% by weight of the total weight of each composition.

The rheology modifier(s) that may be chosen according to variousembodiments of the disclosure include polymers of natural origin andsynthetic polymers, and may optionally be chosen from thoseconventionally used in cosmetics

Non-limiting examples of synthetic polymers that may be used includepolyvinylpyrrolidone, polyacrylic acid, polyacrylamide, non-crosslinkedpoly(2-acryl-amidopropanesulphonic acid) (Simugel™ EG from the companySEPPIC), crosslinked poly(2-acrylamido-2-methylpropanesulphonic acid),free or partially neutralized with ammonia (Hostacerin® AMPS fromClariant), mixtures of non-crosslinkedpoly(2-acrylamido-2-methylpropanesulphonic acid) withhydroxyalkylcellulose ethers or with poly(ethylene oxide)s, such asdescribed in U.S. Pat. No. 4,540,510; mixtures ofpoly((meth)acrylamido(C₁-C₄)alkylsulphonic acid), which is optionallycrosslinked, with a crosslinked copolymer of maleic anhydride and of a(C₁-C₅)alkyl vinyl ether (Hostacerin® AMPS/Stabileze QM from the companyISF).

The polymers of natural origin may include, for example, thickeningpolymers comprising at least one sugar unit, for instance nonionic guargums, optionally modified with C₁-C₆ hydroxyalkyl groups;biopolysaccharide gums of microbial origin, such as scleroglucan gum orxanthan gum; gums derived from plant exudates, such as gum arabic,ghatti gum, karaya gum, gum tragacanth, carrageenan gum, agar gum andcarob gum; pectins; alginates; starches; hydroxy(C₁-C₆)alkylcellulosesand carboxy(C₁-C₆)alkylcelluloses.

It should be noted that the term “sugar unit” denotes a monosaccharide(i.e. monosaccharide or oside or simple sugar) portion, anoligosaccharide portion (short chains formed from a sequence ofmonosaccharide units, which may be different) or a polysaccharideportion [long chains consisting of monosaccharide units, which may bedifferent, i.e. polyholosides or polyosides]. The saccharide units mayalso be substituted with alkyl, hydroxyalkyl, alkoxy, acyloxy orcarboxyl radicals, the alkyl radicals containing from 1 to 4 carbonatoms.

Non-limiting examples of nonionic, unmodified guar gums that may be usedin various embodiments include Guargel D/15 (Noveon); Vidogum GH 175(Unipectine), Meypro-Guar 50 and Jaguar C (Meyhall/Rhodia Chimie).Non-limiting examples of modified nonionic guar gums include Jaguar HP8,HP60, HP120, DC 293 and HP 105 (Meyhall/Rhodia Chimie); Galactasol4H4FD2 (Aqualon).

Among these gums, mention will be made of scleroglucans such as, forexample, Actigum CS from Sanofi Bio Industries; Amigel from Alban MullerInternational, and also the glyoxal-treated scleroglucans described inFR2633940); xanthan gums, for instance Keltrol®, Keltrol® T, Keltrol®Tf, Keltrol® Bt, Keltrol® Rd, Keltrol® Cg (Nutrasweet Kelco), Rhodicare®S and Rhodicare® H (Rhodia Chimie); starch derivatives, for instancePrimogel® (Avebe); hydroxyethylcelluloses such as Cellosize® QP3L,QP4400H, QP30000H, HEC30000A and Polymer PCG10 (Amerchol), Natrosol250HHR®, 250MR, 250M, 250HHXR, 250HHX, 250HR, HX (Hercules) and Tylose®H1000 (Hoechst); hydroxypropylcelluloses, for instance Klucel® EF, H,LHF, MF and G (Aqualon); carboxymethylcelluloses, for instance Blanose®7M8/SF, refined 7M, 7LF, 7MF, 9M31F, 12M31XP, 12M31P, 9M31XF, 7H, 7M31,7H3SXF (Aqualon), Aquasorb® A500 (Hercules), Ambergum® 1221 (Hercules),Cellogen® HP810A, HP6HS9 (Montello) and Primellose® (Avebe).

Associative polymers may be chosen from, by way of example only, thosedescribed in WO11076792, incorporated by reference herein, including butnot limited to associative polyurethanes which are cationic or nonionic,associative cellulose derivatives which are cationic or nonionic,associative vinyllactams, associative unsaturated polyacids, associativeaminoplast ethers, and associative polymers or copolymers comprising atleast one monomer comprising ethylenic unsaturation, and comprising asulpho group.

An example of an associative polyurethanes is methacrylic acid/methylacrylate/ethoxylated (40 EO) behenyl alcoholdimethyl(meta-isopropenyl)benzyl isocyanate terpolymer as a 25 percentaqueous dispersion, known by the trade name, Viscophobe® DB 1000 andcommercially available from Amerchol.

More particularly, preference is given to the use of a polyetherpolyurethane capable of being obtained by polycondensation of at leastthree compounds comprising (i) at least one polyethylene glycolcomprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcoholor decyl alcohol and (iii) at least one diisocyanate.

Such polyether polyurethanes are sold in particular by Rohm and Haasunder the names ACULYN 46® and ACULYN 44® [ACULYN 46® is apolycondensate of polyethylene glycol comprising 150 or 180 mol ofethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexylisocyanate) (SMDI), at 15 percent by weight in a matrix of maltodextrin(4%) and of water (81% ACULYN 44® is a polycondensate of polyethyleneglycol comprising 150 or 180 mol of ethylene oxide, of decyl alcohol andof methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35 percent) byweight in a mixture of propylene glycol (39%) and of water (26%)].

Associative celluloses may also be used, such as quaternized cationiccelluloses and quaternized cationic hydroxyethylcelluloses modified bygroups comprising at least one hydrophobic chain, such as alkyl,arylalkyl or alkylaryl groups comprising at least 8 carbon atoms, orblends thereof.

The alkyl radicals carried by the above quaternized celluloses orhydroxyethylcelluloses may, in various embodiments, comprise from 8 to30 carbon atoms. The aryl radicals may, for example, denote the phenyl,benzyl, naphthyl or anthryl groups.

There may be indicated, as examples, of quaternizedalkylhydroxy-ethylcelluloses comprising a C8-C30 hydrophobic chain, theproducts Quatrisoft LM 200®, Quatrisoft LM-X 529-18-A®, Quatrisoft LM-X529-18B® (C₁₂ alkyl) and Quatrisoft LM-X 529-8® (Ci8 alkyl) sold byAmerchol and the products Crodacel QM®, Crodacel QL® (C12 alkyl) andCrodacel QS® (Ci₈ alkyl) sold by Croda.

Nonionic cellulose derivatives may be chosen, such ashydroxyethylcelluloses modified by groups comprising at least onehydrophobic chain, such as alkyl, arylalkyl or alkylaryl groups, ortheir blends, and in which the alkyl groups are, for example, C₈-C₂₂alkyl groups, such as the product Natrosol Plus Grade 330 CS® (C₁₆alkyls) sold by Aqualon or the product Bermocoll EHM 100® sold by BerolNobel.

Cellulose derivatives modified by alkylphenyl polyalkylene glycol ethergroups may also be chosen, such as the product Amercell Polymer HM-1500®sold by Amerchol.

As regards the associative polyvinyllactams, mention may be made, by wayof example only, of the polymers described in particular in FR 0101106.The said polymers are, for example, cationic polymers. Use may inparticular be made, as poly(vinyllactam) polymers, ofvinylpyrrolidone/dimethylaminopropyl-methacrylamide/dodecyldimethylmethacrylamidopropylammoniumtosylate terpolymers,vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethylmethacrylamidopropylammoniumtosylate terpolymers orvinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethacrylamidopropylammoniumtosylate or chloride terpolymers. Thevinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethacrylamidopropylammoniumchloride terpolymer is provided at 20 percent in water by ISP under thename Styleze® W20.

Associative polyvinyllactam derivatives can also be nonionic copolymersof vinylpyrrolidone and of hydrophobic monomers comprising a hydrophobicchain, for example, the products Antaron V216® or Ganex V2 16®(vinylpyrrolidone/hexadecene copolymer) sold by ISP, or the productsAntaron V220® or Ganex V220® (vinylpyrrolidone/eicosene copolymer) soldby ISP.

Examples of associative polymers comprising an aminoplast ether backboneare the products Pure-Thix® L (PEG-1 80/Octoxynol-40/TMMG Copolymer),Pure-Thix M® (PEG-1 80/Laureth-50/TMMG Copolymer), Pure-Thix® HH(Polyether-1); Pure-Thix TX-1442® (PEG-1 8/dodoxynol-5/PEG-25tristyrylphenol/tetramethoxymethyl-glyco luril copolymer), which areprovided by Sud-Chemie.

Associative polymers may also be chosen from water-soluble thickeningpolymers. In various exemplary embodiments, the at least onerheology-modifying agent may be chosen from thickening polymerscomprising at least one fatty chain, such as described in U.S. Pat. No.7,771,492; thickening polymers chosen from (i) copolymers resulting fromthe polymerization of at least one monomer (a) chosen from carboxylicacids possessing α,β-ethylinic unsaturation or their esters with atleast one monomer (b) possessing ethylinic unsaturation comprising ahydrophobic group, (ii) polymers comprising at least one monomerpossessing a sulpho group, and mixtures thereof, such as described inUS20110088711; rheological agents such as crystalline andsemi-crystalline polymers, esters of dextrin and a fatty acid, modifiedhydrophobic polysaccharides, crystalline olefin copolymers, crystallinepolycondensates, lipophilic miners structure-forming agents, lipophilicpolyamide polymers, lipophilic polyureas and polyurethanes, siliconepolymers, organic gelling agents, block copolymers, silicone elastomers,cholesteric liquid crystal agents, waxes, and mixtures thereof, such asdescribed in US20110200543; and non-associative thickening polymers,such as described in U.S. Pat. No. 7,250,064, the disclosures of whichare all incorporated by reference herein.

In certain exemplary embodiments, the rheology-modifying agents arechosen from cellulose derivatives, polysaccharides, gums, clays, fumedsilica, acrylates, polyacrylamides, crosslinked polyacrylic acids,crosslinked acrylamide polymers and copolymers, crosslinkedmethacryloyloxyethltrimethyl-ammonium chloride homopolymers, andassociative polymers. Said rheology-modifying agents may include, inparticular embodiments, xanthan gum, gum arabic, ghatti gum, karaya gum,gum tragacanth, carrageenan gum, agar gum, carob gum, pectins,alginates, starches, hydroxy(C₁-C₆)alkylcelluloses,carboxy(C₁-C₆)alkylcelluloses, and mixtures thereof.

In various embodiments, the at least one rheology-modifying agent may bepresent in an amount ranging from about 0.1% to about 40% by weight,such as from about 0.1% to about 30% by weight, from about 0.5% to about30% by weight, from about 0.5% to about 25% by weight, or from about 1%to about 20% by weight, based on the total weight of the composition. Inat least one exemplary embodiment, the at least one rheology-modifyingagent may be present in an amount of at least about 1% by weight, basedon the total weight of the composition.

Chelants

Exemplary chelants that may be useful in various embodiments accordingto the disclosure include, but are not limited to,diamine-N,N′-dipolyacid, monoamine monoamide-N,N′-dipolyacid, andN,N′-bis(2-hydroxybenzyl)-ethylenediamine-N,N′-diacetic acid chelants,carboxylic acids (e.g. aminocarboxylic acids), phosphonic acids (e.g.aminophosphonic acids), and polyphosphoric acids (e.g., linearpolyphosphoric acids), and salts and derivatives thereof. Chelants arewell known in the art, and a non-exhaustive list thereof can be found inA E Martell and R M Smith, Critical Stability Constants, Vol. 1, PlenumPress, New York and London (1974), and A E Martell and R D Hancock,Metal Complexes in Aqueous Solution, Plenum Press, New York and London(1996), the disclosures of which are incorporated herein by reference.

As used herein with regard to chelants, the phrase “salts andderivatives thereof” is intended to mean all salts and derivativescomprising the same functional structure as the chelant they arereferring to, and that have similar or better chelating properties.These terms include, for example, alkali metal, alkaline earth,ammonium, substituted ammonium salts (e.g monoethanolammonium,diethanolammonium, triethanolammonium), esters of chelants having anacidic moiety and mixtures thereof, in particular all sodium, potassiumor ammonium salts. The term “derivatives” also includes “chelatingsurfactant” compounds (i.e. chelants modified to bear a surfactantmoiety while keeping the same chelating functionality). The term“derivatives” also includes large molecules comprising one or morechelating groups having the same functional structure as the parentchelants, such as, for example, polymericethylenediamine-N,N′-disuccinic acid (EDDS).

By way of example, aminocarboxylic acid chelants may be chosen fromchelants having at least one carboxylic acid moiety (—COOH) and at leastone nitrogen atom. Non-limiting examples of aminocarboxylic acidchelants suitable for use according to various embodiments of thedisclosure include diethylenetriamine pentaacetic acid (DTPA),ethylenediamine-N,N′-disuccinic acid (EDDS), ethylenediamine diglutaricacid (EDGA), 2-hydroxypropylenediamine disuccinic acid (HPDS),glycinamide-N,N′-disuccinic acid (GADS), ethylenediamine-N—N′-diglutaricacid (EDDG), 2-hydroxypropylenediamine-N—N′-disuccinic acid (HPDDS),ethylenediaminetetraacetic acid (EDTA), ethylenedicysteic acid (EDC),EDDHA (ethylenediamine-N—N′-bis(ortho-hydroxyphenyl acetic acid)),diaminoalkyldi-(sulfosuccinic acids) (DDS),N,N′-bis(2-hydroxybenzyl)ethylenediamine-N,N′-diacetic acid (HBED), andsalts and derivatives thereof.

Other suitable non-limiting aminocarboxylic type chelants areiminodiacetic acid derivatives, such as N-2-hydroxyethyl N,N diaceticacid or glyceryl imino diacetic acid, iminodiaceticacid-N-2-hydroxypropyl sulfonic acid and aspartic acid, N-carboxymethylN-2-hydroxypropyl-3-sulfonic acid, beta-alanine-N,N′-diacetic acid,aspartic acid-N,N′-diacetic acid, aspartic acid-N-monoacetic acid, andiminodisuccinic acid chelants, ethanoldiglycine acid, and salts andderivatives thereof. Dipicolinic acid and2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable.

In various exemplary embodiments, aminophosphonic acid type chelants,salts thereof, derivatives thereof and mixtures thereof, may be chosen.Aminophosphonic acid-type chelants include, for example, chelantscomprising an amino-phosphonic acid moiety (—PO₃H₂) or its derivative—PO₃R2, wherein R2 is a C₁ to C₆ alkyl or aryl radical. Non-limitingaminophosphonic acid-type chelants may be chosen fromaminotri-(1-ethylphosphonic acid),ethylenediaminetetra-(1-ethylphosphonic acid),aminotri-(1-propylphosphonic acid), and aminotri-(isopropylphosphonicacid). In further exemplary embodiments, the aminophosphonic acid typechelant may be chosen from aminotri(methylenephosphonic acid),ethylene-diamine-tetra-(methylenephosphonic acid) (EDTMP),diethylene-triamine-penta-(methylenephosphonic acid) (DTPMP), ormixtures thereof.

Examples of other chelants suitable for use according to embodiments ofthe disclosure include, but are not limited to, quercetinpolyethyleneimines, polyphosphoric acid chelants, editronic acid,methylglycine diacetic acid, N-(2-hydroxyethyl)iminodiacetic acid,iminodisuccinnic acid, N,N-Dicarboxymethyl-L-glutamic acid andN-lauroyl-N,N′,N-ethylenediamine diacetic acid.

In various exemplary embodiments, the compositions comprise one or morechelants chosen from diethylenetriamine pentaacetic acid (DTPA),ethylenediamine-N,N′-disuccinic acid (EDDS),ethylenediamine-N,N′-diglutaric acid (EDDG),2-hydroxypropylenediamine-N,N′-disuccinic acid (HPDDS),glycinamide-N,N′-disuccinic acid (GADS),ethylenediamine-N—N′-bis(ortho-hydroxyphenyl acetic acid) (EDDHA),diethylene-triamine-penta-(methylenephosphonic acid) (DTPMP), saltsthereof, derivatives thereof, or mixtures thereof.

In at least one exemplary embodiment, the chelant may be chosen fromethylenediamine-N,N′-disuccinic acid (EDDS). In at least one furtherexemplary embodiment, the chelant may be chosen from etidronic acid. Invarious embodiments, one or both of these chelants may be chosen fortheir efficiency, safety, and/or biodegradability.

In various embodiments, the at least one chelant may be present in anamount sufficient to reduce the amount of metals available to interactwith formulation components, such as oxidizing agents. By way ofexample, the at least one chelant may be present in an amount up toabout 10% by weight, such as an amount ranging from about 0.01% to about5% by weight, about 0.25% to about 3% by weight, or about 0.5% to about1% by weight, based on the total weight of the composition. In at leastone embodiment, the chelant may be present in an amount of at least0.25%, such as at least 0.5%. In a further exemplary embodiment, thecomposition comprises from about 0.1% to about 5% by weight ofdiethylene-triamine-penta-(methylenephosphonic acid), and from about0.1% to about 5% by weight of ethylenediamine-N,N′-disuccinic acid.

Fatty Substances

Exemplary fatty substances that may be used in various embodiments ofthe disclosure include, but are not limited to, organic compounds thatare insoluble in water at normal temperature (25° C. and at atmosphericpressure (760 mmHg) (solubility below 5% and such as below 1% andfurther such as below 0.1%). Fatty substances have in their structure achain of at least two siloxane groups, or at least one hydrocarbon chainhaving at least 6 carbon atoms. Moreover, fatty substances are generallysoluble in organic solvents in the same conditions of temperature andpressure, for example in chloroform, ethanol, benzene ordecamethylcyclopentasiloxane.

Fatty substances may be, for example, chosen from lower alkanes, fattyalcohols, esters of fatty acid, esters of fatty alcohol, oils such asmineral, vegetable, animal and synthetic non-silicone oils, non-siliconewaxes and silicones.

In some embodiments, the alcohols and esters have at least one linear orbranched, saturated or unsaturated hydrocarbon group, comprising 6 to 30carbon atoms, optionally substituted, for example, with at least onehydroxyl group (for example 1 to 4). If they are unsaturated, thesecompounds can have one to three, conjugated or unconjugated,carbon-carbon double bonds.

With regard to the lower alkanes, in some embodiments, these have from 6to 16 carbon atoms and are linear or branched, optionally cyclic. Asexamples, alkanes can be chosen from hexane and dodecane, isoparaffinssuch as isohexadecane and isodecane.

Examples of non-silicone oils that may be used in various embodiments ofthe disclosure, include, but are not limited to, hydrocarbon oils ofanimal origin, such as perhydrosqualene; hydrocarbon oils of vegetableorigin, such as liquid triglycerides of fatty acids having from 6 to 30carbon atoms such as triglycerides of heptanoic or octanoic acids, orfor example sunflower oil, maize oil, soya oil, cucurbit oil, grapeseedoil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil,sunflower oil, castor oil, avocado oil, triglycerides of caprylic/capricacids such as those sold by the company Stearineries Dubois or thosesold under the names MIGLYOL® 810, 812 and 818 by the company DynamitNobel, jojoba oil, shea butter oil; hydrocarbons with more than 16carbon atoms, linear or branched, of mineral or synthetic origin, suchas paraffin oils, petroleum jelly, liquid paraffin, polydecenes,hydrogenated polyisobutene such as Parleam® fluorinated, partiallyhydrocarbon oils; as fluorinated oils, non-limiting examples includeperfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, soldunder the names “FLUTEC® PC1” and “FLUTEC® PC3” by the company BNFLFluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanessuch as dodecafluoropentane and tetradecafluorohexane, sold under thenames “PF 5050®” and “PF 5060®” by the 3M Company, orbromoperfluorooctyl sold under the name “FORALKYL®” by the companyAtochem; nonafluoro-methoxybutane and nonafluoroethoxyisobutane;derivatives of perfluoromorpholine, such as 4-trifluoromethylperfluoromorpholine sold under the name “PF 5052®” by the 3M Company.

The fatty alcohols that may be chosen as the at least one fattysubstance include, but are not limited to, non-alkoxylated, saturated orunsaturated, linear or branched, and have from 6 to 30 carbon atoms andmore particularly from 8 to 30 carbon atoms. For example, cetyl alcohol,stearyl alcohol and their mixture (cetylstearyl alcohol),octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol,oleic alcohol or linoleic alcohol may be chosen.

The exemplary non-silicone wax or waxes that can be used may be chosenfrom carnauba wax, candelilla wax, Alfa wax, paraffin wax, ozokerite,vegetable waxes such as olive wax, rice wax, hydrogenated jojoba wax, orabsolute waxes of flowers, such as the essential wax of blackcurrantflower sold by the company BERTIN (France), animal waxes such asbeeswaxes, or modified beeswaxes (cerabellina). Further waxes or waxyraw materials usable according to the disclosure are, for example,marine waxes such as that sold by the company SOPHIM under referenceM82, waxes of polyethylene or of polyolefins in general.

The exemplary fatty acid esters are the esters of saturated orunsaturated, linear or branched C₁-C₂₆ aliphatic mono- or polyacids andof saturated or unsaturated, linear or branched C₁-C₂₆ aliphatic mono-or polyalcohols, the total number of carbons of the esters being, forexample, greater than or equal to 10.

Among the monoesters, non-limiting mentions can be made ofdihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyllactate; C₁₂-C₁₅ alkyl lactate; isostearyl lactate; lauryl lactate;linoleyl lactate; oleyl lactate; (iso)stearyl octanoate; isocetyloctanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetylisostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate;isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methylacetyl ricinoleate; myristyl stearate; octyl isononanoate; 2-ethylhexylisononate; octyl palmitate; octyl pelargonate; octyl stearate;octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates,ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, alkyl myristates suchas isopropyl, butyl, cetyl, 2-octyldodecyl, mirystyl, stearyl myristate,hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyllaurate, and 2-hexyldecyl laurate.

Further non-limiting examples of esters include esters of C₄-C₂₂ di- ortricarboxylic acids and of C₁-C₂₂ alcohols and the esters of mono-, di-or tricarboxylic acids and of C₂-C₂₆ di-, tri-, tetra- or pentahydroxyalcohols.

Even further non-limiting examples of esters include: diethyl sebacate;diisopropyl sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyladipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate;octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate;pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate;pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate;propylene glycol dicaprylate; propylene glycol dicaprate, tridecylerucate; triisopropyl citrate; triisotearyl citrate; glyceryltrilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleylcitrate, propylene glycol dioctanoate; neopentyl glycol diheptanoate;diethylene glycol diisanonate; and polyethylene glycol distearates.

Among the esters mentioned above, exemplary esters include ethyl,isopropyl, myristyl, cetyl, stearyl palmitates, ethyl-2-hexyl palmitate,2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl,cetyl, 2-octyldodecyl myristate, hexyl stearate, butyl stearate,isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurateand isononyl isononanate, cetyl octanoate.

The composition can also comprise, as fatty ester, esters and di-estersof sugars of C₆-C₃₀, such as C₁₂-C₂₂ fatty acids. “Sugar” as used heremeans oxygen-containing hydrocarbon compounds that possess severalalcohol functions, with or without aldehyde or ketone functions, andhaving at least 4 carbon atoms. These sugars can be monosaccharides,oligosaccharides or polysaccharides.

As suitable sugars, non-limiting examples include sucrose, glucose,galactose, ribose, fucose, maltose, fructose, mannose, arabinose,xylose, lactose, and their derivatives, for example alkylated, such asmethylated derivatives such as methylglucose.

The esters of sugars and of fatty acids may be, for example, chosen fromthe esters or mixtures of esters of sugars described previously and oflinear or branched, saturated or unsaturated C₆-C₃₀, such as C₁₂-C₂₂fatty acids. If they are unsaturated, these compounds can have one tothree, conjugated or unconjugated, carbon-carbon double bonds.

The esters according to at least one embodiment can also be chosen frommono-, di-, tri- and tetra-esters, polyesters and mixtures thereof.

These esters can be, for example, oleate, laurate, palmitate, myristate,behenate, cocoate, stearate, linoleate, linolenate, caprate,arachidonates, or mixtures thereof such as the oleo-palmitate,oleo-stearate, palmito-stearate mixed esters.

For example, the mono- and di-esters can be used, and such as the mono-or di-oleate, stearate, behenate, oleopalmitate, linoleate, linolenate,oleostearate, of sucrose, of glucose or of methylglucose.

One non-limiting example useful in various embodiments includes theproduct sold under the name GLUCATE® DO by the company Amerchol, whichis a dioleate of methylglucose.

Exemplary esters or mixtures of esters of sugar of fatty acid include:the products sold under the names F160, F140, F110, F90, F70, SL40 bythe company Crodesta, denoting respectively the palmito-stearates ofsucrose formed from 73% of monoester and 27% of di- and tri-ester, from61% of monoester and 39% of di-, tri-, and tetra-ester, from 52% ofmonoester and 48% of di-, tri-, and tetra-ester, from 45% of monoesterand 55% of di-, tri-, and tetra-ester, from 39% of monoester and 61% ofdi-, tri-, and tetra-ester, and the mono-laurate of sucrose; theproducts sold under the name Ryoto Sugar Esters for example with thereference B370 and corresponding to the behenate of sucrose formed from20% of monoester and 80% of di-triester-polyester; sucrosemono-di-palmito-stearate marketed by the company Goldschmidt under thename TEGOSOFT® PSE.

Silicones usable in the composition of the present disclosure includebut are not limited to volatile or non-volatile, cyclic, linear orbranched silicones, modified or not with organic groups, having aviscosity from 5×10⁻⁶ to 2.5 m²/s at 25° C., such as from 1×10⁻⁵ to 1m²/s.

The silicones usable according to the disclosure can be in the form ofoils, waxes, resins or gums.

In some embodiments, the silicone may be chosen from thepolydialkylsiloxanes, such as the polydimethylsiloxanes (PDMS), and theorganomodified polysiloxanes having at least one functional group chosenfrom the poly(alkoxylated) groups, the amine groups and the alkoxygroups.

The organopolysiloxanes are defined in more detail in the work of WalterNOLL “Chemistry and Technology of Silicones” (1968), Academic Press.They can be volatile or non-volatile.

When they are volatile, the silicones are, for example, chosen fromthose with a boiling point between 60° C. and 260° C. By way of example,the silicones may be chosen from cyclic polydialkylsiloxanes having from3 to 7, such as from 4 to 5, silicon atoms. Various exemplary siliconesmay be the octamethylcyclotetrasiloxane marketed under the name VOLATILESILICONE® 7207 by UNION CARBIDE or SILBIONE® 70045 V2 by RHODIA, thedecamethylcyclopentasiloxane marketed under the name VOLATILE SILICONE®7158 by UNION CARBIDE, and SILBIONE® 70045 V5 by RHODIA, and mixturesthereof.

Non-limiting examples may also include the cyclocopolymers of thedimethylsiloxanes/methylalkylsiloxane type, such as SILICONE VOLATILE®FZ 3109 marketed by the company UNION CARBIDE, of the following formula(II):

with D″:

with D′:

Further non-limiting examples may include mixtures of cyclicpolydialkylsiloxanes with organic compounds derived from silicon, suchas the mixture of octamethylcyclotetrasiloxane andtetratrimethylsilylpentaerythritol (50/50) and the mixture ofoctamethylcyclotetrasiloxane andoxy-1,1′-(hexa-2,2,2′,2′,3,3′-trimethylsilyloxy)bis-neopentane.

Other suitable volatile silicones include the linear volatilepolydialkylsiloxanes having 2 to 9 silicon atoms and with a viscosityless than or equal to 5×10⁻⁶ m²/s at 25° C. One non-limiting example isdecamethyltetrasiloxane, marketed under the name “SH 200” by the companyTORAY SILICONE. Silicones included in this class are also described inthe article published in Cosmetics and Toiletries, Vol. 91, January 76,p. 27-32-TODD BYERS “Volatile Silicone fluids for cosmetics,” which isincorporated by reference herein.

Even further non-limiting mentions can be made of non-volatilepolydialkylsiloxanes, gums and resins of polydialkylsiloxanes,polyorganosiloxanes modified with the aforementioned organofunctionalgroups, and mixtures thereof.

These silicones may be, for example, chosen from thepolydialkylsiloxanes, such as the polydimethylsiloxanes withtrimethylsilyl end groups. The viscosity of the silicones is measured at25° C. according to Standard Test Method for Kinematic Viscosity ofTransparent and Opaque Liquids (and Calculation of Dynamic Viscosity).

Among these polydialkylsiloxanes, mention can be made of,non-exhaustively, the following commercial products: the SILBIONE® oilsof series 47 and 70 047 or the MIRASIL® oils marketed by RHODIA, forexample the oil 70 047 V 500,000; the oils of the MIRASIL® seriesmarketed by the company RHODIA; the oils of the 200 series from thecompany DOW CORNING such as DC200, with a viscosity of 60,000 mm²/s; theVISCASIL® oils from GENERAL ELECTRIC and certain oils of the SF series(SF 96, SF 18) from GENERAL ELECTRIC.

Non-limiting mention can also be made of the polydimethylsiloxanes withdimethylsilanol end groups known under the name of dimethiconol (CTFA),such as the oils of the 48 series from the company RHODIA.

In this class of polydialkylsiloxanes, non-limiting mentions can be madeof the products marketed under the names “ABIL WAX® 9800 and 9801” bythe company GOLDSCHMIDT, which are polydialkyl (C₁-C₂₀) siloxanes.

The silicone gums usable according to the disclosure are, for example,polydialkylsiloxanes, such as polydimethylsiloxanes with highnumber-average molecular weights between 200,000 and 1,000,000 usedalone or mixed in a solvent. This solvent can be chosen from thevolatile silicones, the polydimethylsiloxane (PDMS) oils, thepolyphenylmethylsiloxane (PPMS) oils, the isoparaffins, thepolyisobutylenes, methylene chloride, pentane, dodecane, tridecane andmixtures thereof.

Products useful according to various embodiments of the disclosureinclude, for example, mixtures such as those formed from a chain endhydroxylated polydimethylsiloxane, or dimethiconol (CTFA) and a cyclicpolydimethylsiloxane also called cyclomethicone (CTFA), such as theproduct Q2 1401 marketed by the company DOW CORNING; mixtures of apolydimethylsiloxane gum and a cyclic silicone such as the product SF1214 Silicone Fluid from the company GENERAL ELECTRIC, said productbeing a gum SF 30 corresponding to a dimethicone, having anumber-average molecular weight of 500,000, dissolved in the oil SF 1202Silicone Fluid corresponding to decamethylcyclopentasiloxane; mixturesof two PDMS of different viscosities, for example, of a PDMS gum and aPDMS oil, such as the product SF 1236 from the company GENERAL ELECTRIC.The product SF 1236 is a mixture of a gum SE 30 as defined above havinga viscosity of 20 m²/s and an oil SF 96 with a viscosity of 5×10⁻⁶ m²/s.This product, for example, has 15% of gum SE 30 and 85% of oil SF 96.

The organopolysiloxane resins usable according to the disclosureinclude, but are not limited to, crosslinked siloxane systems containingthe units: R₂SiO_(2/2), R₃SiO_(1/2), RSiO_(3/2) and SiO_(4/2), wherein Rrepresents an alkyl having from 1 to 16 carbon atoms. For example, R maydenote a C₁-C₄ lower alkyl group, such as methyl.

Among these resins, non-limiting mention can be made of the productmarketed under the name “DOW CORNING® 593” or those marketed under thenames “SILICONE FLUID SS 4230 and SS 4267” by the company GENERALELECTRIC, which are silicones of dimethyl/trimethyl siloxane structure.

Non-limiting mention can also be made of the resins of thetrimethylsiloxysilicate type, such as those marketed under the namesX22-4914, X21-5034 and X21-5037 by the company SHIN-ETSU.

The organomodified silicones usable according to the disclosure includebut are not limited to silicones as defined previously, having in theirstructure at least one organofunctional group fixed by a hydrocarbongroup.

In addition to the silicones described above, the organomodifiedsilicones can be polydiaryl siloxanes, such as polydiphenylsiloxanes,and polyalkylarylsiloxanes functionalized by the aforementionedorganofunctional groups.

The polyalkarylsiloxanes are, for example, chosen from thepolydimethyl/methylphenylsiloxanes, the polydimethyl/diphenylsiloxanes,linear and/or branched, with viscosity ranging from 1×10⁻⁵ to 5×10² m²/sat 25° C.

Among these polyalkarylsiloxanes, non-limiting mention can be made ofthe products marketed under the following names: the SILBIONE® oils ofseries 70 641 from RHODIA; the oils of the series RHODORSIL® 70 633 and763 from RHODIA; the oil DOW CORNING® 556 COSMETIC GRADE FLUID from DOWCORNING; the silicones of the PK series from BAYER such as the productPK20; the silicones of the series PN, PH from BAYER such as the productsPN1000 and PH1000; certain oils of the SF series from GENERAL ELECTRICsuch as SF 1023, SF 1154, SF 1250, SF 1265.

Among the organomodified silicones, non-limiting mention can be made ofthe polyorganosiloxanes having: polyoxyethylene and/or polyoxypropylenegroups optionally with C₆-C₂₄ alkyl groups such as the products calleddimethicone copolyol marketed by the company DOW CORNING under the nameDC 1248 or the oils SILWET® L 722, L 7500, L 77, L 711 from the companyUNION CARBIDE and the alkyl (C₁₂)-methicone copolyol marketed by thecompany DOW CORNING under the name Q2 5200; substituted or unsubstitutedamine groups such as the products marketed under the name GP 4 SiliconeFluid and GP 7100 by the company GENESEE or the products marketed underthe names Q2 8220 and DOW CORNING® 929 or 939 by the company DOWCORNING. The substituted amine groups are, for example, C₁-C₄ aminoalkylgroups; alkoxylated groups, such as the product marketed under the name“SILICONE COPOLYMER F-755” by SWS SILICONES and ABIL WAX® 2428, 2434 and2440 by the company GOLDSCHMIDT.

In various exemplary embodiments, the at least one fatty substance isneither alkoxylated, nor glycerolated. For example, the at least onefatty substance may be chosen from compounds that are liquid or pasty atroom temperature and atmospheric pressure. By way of example, the atleast one fatty substance may be a compound that is liquid at atemperature of 25° C., and atmospheric pressure.

Exemplary fatty substances may be, for example, chosen from the loweralkanes, fatty alcohols, esters of fatty acid, esters of fatty alcohol,and oils such as non-silicone mineral, vegetable and synthetic oils, thesilicones.

According to at least one embodiment, the at least one fatty substanceis chosen from liquid paraffin, polydecenes, liquid esters of fattyacids and of fatty alcohols, and mixtures thereof, for example, the atleast one fatty substance of the composition according to the disclosurecan be non-silicone.

In some embodiments, the at least one fatty substance is chosen fromalkanes, hydrocarbons and silicones.

In further exemplary embodiments, the at least one fatty substance maybe chosen from fatty acids. By way of example only, fatty acids havingfrom about 6 to about 40 carbon atoms may be chosen, including but notlimited to Arachidic Acid, Arachidonic Acid, Beeswax Acid, Capric Acid,Caproic Acid, Caprylic Acid, Coconut Acid, Isostearic Acid, Lauric Acid,Linoleic Acid, Linolenic Acid, Myristic Acid, Oleic Acid, Olive Acid,Palmitic Acid, Rapeseed Acid, Stearic Acid, Tallow Acid, UndecanoicAcid, Undecylenic Acid, Wheat Germ Acid.

In various exemplary embodiments, fatty acids having from about 6 toabout 40 carbon atoms are chosen from Capric Acid, Caprylic Acid, LauricAcid, Oleic Acid, Isostearic Acid, and Stearic Acid.

In various embodiments, the at least one fatty substance may be presentin an amount of at least about 10% by weight, such as from about 10% toabout 80% by weight, such as from about 15% to about 65% by weight, orfrom about 20% to about 55% by weight, based on the total weight of thecomposition.

Ceramides

Ceramide compounds that may be useful according to various embodimentsinclude ceramides, glycoceramides, pseudoceramides, and mixturesthereof. The ceramides which may be used include, but are not limitedto, those described by DOWNING in Arch. Dermatol, Vol. 123, 1381-1384(1987), DOWNING in Journal of Lipid Research, Vol. 35, page 2060 (1994),or those described in French patent FR 2673179, all of which areincorporated by reference herein.

Further exemplary ceramides that may be used according to variousembodiments of the disclosure include, but are not limited to, compoundsof the general formula (III):

wherein, in formula (III):

-   -   R₁₈ and R₁₉ are, independently, chosen from alkyl- or alkenyl        groups with 10 to 22 carbon atoms,    -   R₂₀ is chosen from methyl, ethyl, n-propyl or isopropyl groups,        and    -   n is a number ranging from 1 to 6, such as, for example, 2 or 3.

In further embodiments, ceramide compounds may be chosen from compoundsof formula (IV), as described in US20050191251 and US20090282623, bothof which are incorporated by reference herein:

wherein, in formula (IV):

-   -   R₁ is chosen from either a saturated or unsaturated, linear or        branched C₁-C₅₀, e.g. C₅-C₅₀, hydrocarbon radical, it being        possible for this radical to be substituted with one or more        hydroxyl groups optionally esterified with an acid R₇COOH, R₇        being an optionally mono- or polyhydroxylated, linear or        branched, saturated or unsaturated C₁-C₃₅ hydrocarbon radical,        it being possible for the hydroxyl(s) of the radical R₇ to be        esterified with an optionally mono- or polyhydroxylated, linear        or branched, saturated or unsaturated C₁-C₃₅ fatty acid, or a        radical R″—(NR—CO)—R′, R being chosen from a hydrogen atom or a        mono- or polyhydroxylated, e.g. monohydroxylated, C₁-C₂₀        hydrocarbon radical, R′ and R″ chosen from, independently,        hydrocarbon radicals of which the sum of the carbon atoms is        between 9 and 30, R′ being a divalent radical, or a radical        R₈—O—CO—(CH₂)p, R₈ denoting a C₁-C₂₀ hydrocarbon radical, p        being an integer varying from 1 to 12;    -   R₂ being chosen from a hydrogen atom, a saccharide-type radical,        in particular a (glycosyl)n, (galactosyl)m and sulphogalactosyl        radical, a sulphate or phosphate residue, a phosphorylethylamine        radical and a phosphorylethylammonium radical, in which n is an        integer varying from 1 to 4 and m is an integer varying from 1        to 8;    -   R₃ chosen from a hydrogen atom or a hydroxylated or        nonhydroxylated, saturated or unsaturated, C₁-C₃₃ hydrocarbon        radical, it being possible for the hydroxyl(s) to be esterified        with an inorganic acid or an acid R₇COOH, R₇ having the same        meanings as above, and it being possible for the hydroxyl(s) to        be etherified with a (glycosyl)n, (galactosyl)m,        sulphogalactosyl, phosphorylethylamine or        phosphorylethylammonium radical, it being also possible for R₃        to be substituted with one or more C₁-C₁₄ alkyl radicals;    -   R₄ being chosen from a hydrogen atom, a methyl or ethyl radical,        an optionally hydroxylated, linear or branched, saturated or        unsaturated C₃-C₅₀ hydrocarbon radical or a radical        —CH₂—CHOH—CH₂—O—R₆ in which R₆ denotes a C₁₀-C₂₆ hydrocarbon        radical or a radical R₈—O—CO—(CH₂)p, R₈ chosen from a C₁-C₂₀        hydrocarbon radical, p being an integer varying from 1 to 12;        and    -   R₅ denotes a hydrogen atom or an optionally mono- or        polyhydroxylated, linear or branched, saturated or unsaturated        C₁-C₃₀ hydrocarbon radical, it being possible for the        hydroxyl(s) to be etherified with a (glycosyl)n, (galactosyl)m,        sulphogalactosyl, phosphorylethylamine or        phosphorylethylammonium radical,    -   with the proviso that when R₃ and R₅ denote hydrogen or when R₃        denotes hydrogen and R₅ denotes methyl, then R₄ does not denote        a hydrogen atom, or a methyl or ethyl radical.

By way of example, ceramides of formula (IV) may be chosen from thosewherein R₁ is an optionally hydroxylated, saturated or unsaturated alkylradical derived from C₁₄-C₂₂ fatty acids; R₂ is a hydrogen atom; and R₃is an optionally hydroxylated, saturated, linear C₁₁-C₁₇, e.g. C₁₃-C₁₅radical.

In yet further embodiments, ceramide compounds useful according to thedisclosure may be chosen from compounds of the general formula (V):

wherein, in formula (V):

-   -   R₁ is chosen from a linear or branched, saturated or unsaturated        alkyl group, derived from C₁₄-C₃₀ fatty acids, it being possible        for this group to be substituted with a hydroxyl group in the        alpha-position, or a hydroxyl group in the omega-position        esterified with a saturated or unsaturated C₁₆-C₃₀ fatty acid;    -   R₂ is chosen from a hydrogen atom or a (glycosyl)_(n),        (galactosyl)_(m) or sulphogalactosyl group, in which n is an        integer ranging from 1 to 4 and m is an integer ranging from 1        to 8; and    -   R₃ is chosen from a C₅-C₂₆ hydrocarbon-based group, saturated or        unsaturated in the alpha-position, it being possible for this        group to be substituted with one or more C₁-C₁₄ alkyl groups; it        being understood that, in the case of natural ceramides or        glycoceramides, R₃ may also be chosen from a C₅-C₂₆        alpha-hydroxyalkyl group, the hydroxyl group being optionally        esterified with a C₁₆-C₃₀ alpha-hydroxy acid.

Exemplary ceramides of formula (V) which may be chosen include compoundswherein R₁ is chosen from a saturated or unsaturated alkyl derived fromC₆-C₂₂ fatty acids; R₂ is chosen from a hydrogen atom; and R₃ is chosenfrom a linear, saturated C₁₅ group. By way of non-limiting example, suchcompounds may be chosen from N-linoleoyldihydrosphingosine,N-oleoyldihydrosphingosine, N-palmitoyldihydro-sphingosine,N-stearoyldihydrosphingosine, N-behenoyldihydrosphingosine, or mixturesthereof.

As further non-limiting examples of ceramides, compounds wherein R₁ ischosen from a saturated or unsaturated alkyl group derived from fattyacids; R₂ is chosen from a galactosyl or sulphogalactosyl group; and R₃is chosen from the group —CH═CH—(CH₂)₁₂—CH₃ group, may be used. In atleast one exemplary embodiment, the product consisting of a mixture ofthese compounds, sold under the trade name Glycocer, by the companyWaitaki International Biosciences, may be used.

As further exemplary ceramides, mention may be made of the followingceramides, as described in US20110182839, incorporated by referenceherein:

In further embodiments, ceramide compounds useful according to thedisclosure may be chosen from compounds of the general formula (VI):

wherein, in formula (VI):

-   -   R₁₁ and R₁₂ are, independently, chosen from alkyl or alkenyl        groups with 10 to 22 carbon atoms,    -   R₁₃ is an alkyl or hydroxyl alkyl group with 1 to 4 carbon        atoms, and    -   n is a number ranging from 1 to 6, such as, for example, 2 or 3.

In at least one embodiment, the at least one ceramide compound is chosenfrom cetyl-PG-hydroxyethylpalmitamide. In a further embodiment, the atleast one ceramide compound is chosen from propanediamide,N,N-dihexadecyl-N,N-bis-(2-hydroxyethyl), such as that sold commerciallyas Questamide H or Pseudoceramide H by the company Quest InternationalAustralia Pty. Ltd. In yet a further embodiment, the at least oneceramide compound is chosen from Cetyl-PG Hydroxylpalmatide/decylglucoside/water, sold as SOFCARE P100H by Kao.

Without wishing to be bound, in at least certain exemplary embodiments,ceramides may be chosen as auxiliary ingredients for their conditioningand/or color-enhancing benefits.

In various embodiments, the at least one ceramide may be present in anamount ranging from about 0.01% to about 2% by weight, such as fromabout 0.01% to about 1% by weight, based on the total weight of thecomposition.

Alkoxyaminosilicones

Exemplary alkoxyaminosilicones that may be used according to thedisclosure include, but are not limited to, alkoxyaminosilicones of thegeneral formula (VII):

wherein, in formula (VII):

-   -   n is a number ranging from about 0 to about 999, such as, for        example, from about 49 to about 249, such as from about 125 to        about 175;    -   m is a number ranging from about 1 to about 1000, such as, for        example, from about 1 to about 10, such as from about 1 to about        5; and    -   m and n are numbers with a sum (n+m) ranging, for example, from        about 1 to about 1000, such as, for example, from about 50 to        about 250 and still further, for example, from about 100 to        about 200; wherein    -   R₁, R₂ and R₃, are independently chosen from a hydroxyl radical        and C₁-C₄ alkoxy radicals, wherein at least one of the radicals        R₁, R₂ and R₃ are chosen from alkoxy radicals.

The alkoxy radical may be, for example, a methoxy radical.

The hydroxy/alkoxy molar ratio may, for example, range from about 0.2:1to about 0.4:1, such as, for example, from about 0.25:1 to about 0.35:1and further, for example, may be equal to about 0.3.

The at least one aminosilicone of formula (VII) may have aweight-average molecular mass ranging, for example, from 2000 to1,000,000, for example from 3500 to 200,000.

By way of example only, the alkoxyaminosilicone product provided by thecompany Wacker under the name Belsil ADM 652®, may be chosen.

Further exemplary alkoxyaminosilicones that may be used according to thedisclosure include, but are not limited to, alkoxyaminosilicones of thegeneral formula (VIII):

wherein, in formula (VIII):

-   -   p is a number ranging from 0 to 999, for example from 49 to 349,        and further, for example, from 159 to 239;    -   q is a number ranging from 1 to 1000, for example, from 1 to 10,        and further, for example, from 1 to 5; and    -   p and q are numbers with a sum (p+q), for example, ranging from        1 to 1000, for example from 50 to 350 and further, for example,        from 150 to 250;    -   R₁ and R₂ are independently chosen from a hydroxyl radical and        C₁-C₄ alkoxy radicals, wherein at least one of the radicals R₁        and R₂ are chosen from alkoxy radicals.

The alkoxy radical may be, for example, a methoxy radical.

The hydroxy/alkoxy molar ratio may, for example, range from about 1:0.8to about 1:1.1, such as, for example from about 1:0.9 to about 1:1, andmay further, for example, be about 1:0.95.

The at least one aminosilicone of formula (VIII) may have aweight-average molecular mass ranging, for example, from 2000 to200,000, for example from 5000 to 100,000, and further, for example,from 10,000 to 50,000.

The weight-average molecular mass of the at least one aminosilicone aremeasured by gel permeation chromatography (GPC) at ambient temperaturein polystyrene equivalents. The columns used are μ Styragel columns. Theeluent is THF and the flow rate is 1 ml/min. 200 μl of a 0.5% by weightsolution of silicone in THF are injected. Detection may be carried outby refractometry and UV metry.

By way of example only, the alkoxyaminosilicone products provided by thecompany Wacker under the name Fluid WR 1300® and Belsil ADM 6057® may bechosen.

The at least one aminosilicone chosen from formulae (VII) and (VIII) maybe employed, for example, in an oil-in-water emulsion. The oil-in-wateremulsion may further comprise at least one surfactant. The at least onesurfactant may be chosen, for example, from cationic and non-ionicsurfactants.

A particle of the at least one aminosilicone in the emulsion may have anaverage size ranging from, for example, about 3 to about 500 nanometres.Such particle sizes are measured with a laser granulometer particle ofthe at least one aminosilicone in the emulsion may have an average sizeranging, for example, from about 3 to about 500 nanometres. Suchparticle sizes are measured with a laser granulometer.

The at least one aminosilicone of formula (VIII) may be used, forexample, in a microemulsion. In the microemulsion, the at least oneaminosilicone of formula (VIII) may have a size ranging from 5 to 60nanometres and, for example, from 10 to 50 nanometres.

A microemulsion of the at least one aminosilicone of formula (VIII) maybe available, for example, under the name Finish CT 96 E® or SLM 28020®by the company Wacker.

The at least one aminosilicone chosen from formulae (VII) and (VIII) maybe selected, for example, such that the contact angle with water of ahair treated with a composition comprising 2% AS (active substance) ofthe at least one aminosilicone ranges from 90° C. to 180° C., forexample from 90° C. to 130° C.

A composition comprising the at least one aminosilicone chosen fromformulae (VII) and (VIII) may be such that the contact angle of a hairtreated with the composition ranges from 90° C. to 180° C., for examplefrom 90° C. to 130° C.

The measurement of the contact angle described herein may be performedas described in U.S. Pat. No. 6,846,333, incorporated by referenceherein. For example, the product SLM 28020® from Wacker at 12% in water(i.e. 2% of at least one aminosilicone) gives a contact angle of 93° C.

In at least certain exemplary embodiments, the alkoxyaminosilicone maybe provided as part of the composition Wacker-Belsil ADM Log 1® (WackerChemie AG (Munich, Germany)), which consists of amodimethicone at 15%,Glycerin at 3.5%, Trideceth-5 at 6% and Trideceth-10 at 1.5%, or as partof the cationic aqueous emulsion Dow Corning 2-8299 Cationic Emulsion(Dow Corning).

Without wishing to be bound, in at least certain exemplary embodiments,alkoxyaminosilicones may be chosen as auxiliary ingredients for theirconditioning, fade-resistance, and/or porosity-reducing benefits, and/orfor their ability to impart improved cosmetic properties to the hair,such as, for example, softness, smoothness, and/or ease of disentanglingand styling.

In various embodiments, the at least one alkoxyaminosilicone may bepresent in an amount ranging from about 0.01% to about 20% by weight,such as from about 0.1% to about 15% by weight, from about 0.5% to about10% by weight, based on the total weight of the composition.

Silane Compounds

Exemplary silanes that may be used according to various embodiments ofthe disclosure include, but are not limited to, organosilanes andderivatives thereof, such as alkylsilanes, allylsilanes, alkoxysilanes,and the like.

In various exemplary embodiments, the at least one silane compound maybe chosen from alkoxysilanes comprising at least one solubilizingfunctional group. By way of non-limiting examples, silanes may be chosenfrom methoxysilanes, triethoxysilanes, and the like such asaminopropyltriethoxysilane, methyltriethoxysilane, and derivativesthereof.

As used herein, the term “at least one solubilizing functional group”means any functional chemical group facilitating the bringing intosolution of the alkoxysilane in the solvent or in a combination ofsolvents of the composition, for example, in solvents chosen from water,water-alcoholic mixtures, organic solvents, polar solvents and non-polarsolvents.

Suitable solubilizing functional groups include, but are not limited to,primary, secondary, and tertiary amine, aromatic amine, alcohol,carboxylic acid, sulfonic acid, anhydride, carbamate, urea, guanidine,aldehyde, ester, amide, epoxy, pyrrole, dihydroimidazole, gluconamide,pyridyle, and polyether groups.

The at least one alkoxysilane comprising at least one solubilizingfunctional group present in the composition may, in at least oneembodiment, comprise two or three alkoxy functions. In anotherembodiment, the alkoxy functional groups are chosen from methoxy andethoxy functional groups.

According to a further embodiment, the at least one alkoxysilanecomprising at least one solubilizing functional group present in thecomposition of the present disclosure is chosen from compounds offormula (IX):

wherein, in formula (IX):

-   -   R₄ is chosen from halogen atoms, OR′ groups, and R₁₁ groups;    -   R₅ is chosen from halogen atoms, OR″ groups, and R₁₂ groups;    -   R₆ is chosen from halogen atoms, OR′″ groups, and R₁₃ groups;    -   R₁, R₂, R₃, R′, R″, R′″, R₁₁, R₁₂, and R₁₃, which may be        identical or different, are chosen from linear and branched,        saturated and unsaturated hydrocarbon groups, optionally bearing        at least one additional chemical group, wherein R₁, R₂, R′, R″,        and R′″ may also be chosen from hydrogen; at least two groups        R₄, R₅, and R₆ are different from R₁₁, R₁₂, and R₁₃, and at        least two groups R′, R″, and R′″ are not hydrogen.

The at least one alkoxysilane comprising at least one solubilizingfunctional group may also be chosen from compounds of formula (X):

wherein, in formula (X):

-   -   R₉ is chosen from halogen atoms and OR′₉ groups and R₁₀ is        chosen from halogen atoms and OR′₁₀ groups; wherein at least one        of R₉ and R₁₀ is not a halogen;    -   R′₉ and R′₁₀, which may be identical or different, are chosen        from hydrogen, and linear and branched, saturated and        unsaturated C₁-C₁₄ hydrocarbon groups; wherein at least one of        R₉ and R₁₀ is not hydrogen;    -   R₇ is a non hydrolyzable functional group providing a cosmetic        effect, and    -   R₈ is a non hydrolyzable functional group bearing at least one        function chosen from: amines, carboxylic acids and salts        thereof, sulfonic acids and salts thereof, polyols such as        glycol, polyethers such as polyalkylene ether, and phosphoric        acids and salts thereof.

As used herein, the term “functional group providing a cosmetic effect”means a group derived from an entity chosen from reducing agents,oxidizing agents, coloring agents, polymers, surfactants, antibacterialagents, and UV absorbing filters.

According to a third embodiment, the at least one alkoxysilanecomprising at least one solubilizing functional group may be chosen fromcompounds of formula (XI):

wherein, in formula (XI):

-   -   R₁₂ is chosen from halogen atoms, OR′₁₂ groups, and R_(O)        groups;    -   R₁₃ is chosen from halogen atoms, OR′₁₃ groups, and R′_(O)        groups;    -   R₁₄ is chosen from halogen atoms, OR′₁₄ groups, and R″_(O)        groups;    -   wherein at least two groups R₁₂, R₁₃ and R₁₄ are different from        R_(O), R′_(O), and R″_(O) groups;    -   R₁₁ is a group chosen from groups bearing at least one function        chosen from: carboxylic acids and salts thereof, sulfonic acids        and salts thereof, and polyalkylethers; and    -   Ro, R′o, R″o, R′₁₂, R′₁₃, and R′₁₄, which may be identical or        different, are chosen from linear and branched, saturated and        unsaturated, C₁-C₁₄ hydrocarbon groups optionally bearing at        least one additional chemical functional group chosen from:        carboxylic acids and salts thereof, sulfonic acids and salts        thereof, and polyalkylether functions, wherein R′₁₂, R′₁₃, and        R₁₄ may also be chosen from hydrogen, and wherein at least two        of the groups R′₁₂, R′₁₃, and R′₁₄ are not hydrogen.

According to another embodiment, the at least one alkoxysilanecomprising at least one solubilizing functional group may be chosen fromcompounds of formula (XII):

(R₂₁O)_(x)(R₂₂)_(y)Si-(A)_(p)-[NR₂₃-(A′)_(p′)]_(q)-[NR′₂₃-(A″)_(p″)]_(q′)-Si—(R′₂₂)_(y′)(OR′₂₁)_(x′)

wherein, in formula (XII):

-   -   R₂₁, R₂₂, R′₂₁, and R′₂₂, which may be identical or different,        are chosen from linear and branched, saturated and unsaturated        hydrocarbon chains, optionally comprising at least one        heteroatom, optionally interrupted by or substituted with at        least one group chosen from ether, ester, amine, amide,        carboxyl, hydroxyl, and carbonyl groups,    -   x is an integer ranging from 1 to 3,    -   y=3-x,    -   x′ is an integer ranging from 1 to 3,    -   y′=3-x′,    -   p, p′, p″, q, and q′ can each be 0 or 1, wherein at least one of        q or q′ is not equal to zero,    -   A, A′, and A″, which may be identical or different, are chosen        from linear and branched C₁-C₂₀ alkylene divalent radicals, and    -   R₂₃ and R′₂₃, which may be identical or different, are chosen        from hydrogen and linear and branched, saturated and unsaturated        hydrocarbon chains, optionally comprising at least one        heteroatom, optionally interrupted by or substituted with at        least one entity chosen from: ether, C₁-C₂₀ alcohol ester,        amine, carboxyl, alkoxysilane, C₆-C₃₀ aryl, hydroxyl, and        carbonyl groups, and aromatic, heterocyclic, and        non-heterocyclic rings, optionally substituted with at least one        group chosen from C₃-C₂₀ alcohol ester, amine, amide, carboxyl,        alkoxysilane, hydroxyl, carbonyl, and acyl groups.

The at least one alkoxysilane comprising at least one solubilizingfunctional group may also be chosen from compounds of formula (XIII):

wherein, in formula (XIII):

-   -   R₂₄ and R₂₅, which may be identical or different, are chosen        from linear and branched, saturated and unsaturated hydrocarbon        chains, optionally comprising at least one heteroatom,        optionally interrupted by or substituted with at least one group        chosen from ether, ester, amine, amide, carboxyl, hydroxyl, and        carbonyl groups,    -   x″=2 or 3,    -   y″=3-x″,    -   n′=0 or 1,    -   n″=0 or 1,    -   E and E′, which may be identical or different, are chosen from        linear and branched C₁-C₂₀ alkylene divalent radicals,    -   R₂₆ and R₂₇, which may be identical or different, are chosen        from hydrogen and linear and branched, saturated and unsaturated        hydrocarbon chains, optionally comprising at least one        heteroatom, optionally interrupted by or substituted with at        least one entity chosen from: ether, C₁-C₂₀ alcohol ester,        amine, carboxyl, alkoxysilane, C₆-C₃₀ aryl, hydroxyl, and        carbonyl groups, and aromatic, heterocyclic, and        non-heterocyclic rings, optionally substituted with at least one        group chosen from: C₁-C₂₀ alcohol ester, amine, amide, carboxyl,        alkoxysilane, hydroxyl, carbonyl, and acyl groups,    -   r is an integer ranging from 0 to 4,    -   r′=0 or 1, and    -   R₂₈, which may be identical or different, is chosen from        hydrogen and linear and branched, saturated and unsaturated        hydrocarbon chains, comprising, optionally at least one        heteroatom, optionally interrupted by or substituted with at        least one entity chosen from: ether, alkyl alcohol ester, amine,        carboxyl, alkoxysilane, alkyl aryl, hydroxyl, and carbonyl        groups, and aromatic, heterocyclic, and non-heterocyclic rings.

According to a further exemplary embodiment, the at least onealkoxysilane comprising at least one solubilizing functional group maybe chosen from compounds of formula (XIV):

(R₂₉O)x ₁(R₃₀)y ₁-Si-(A₁)_(s)-CH═O

wherein, in formula (XIV):

-   -   R₂₉ and R₃₀, independently, are chosen from linear and branched,        saturated and unsaturated hydrocarbon chains, optionally        comprising at least one heteroatom, optionally interrupted by or        substituted with at least one group chosen from ether, ester,        amine, amide, carboxyl, hydroxyl, and carbonyl groups,    -   x₁=2 or 3,    -   y₁=3-x₁,    -   A₁ is chosen from linear and branched C₁-C₂₀ alkylene divalent        radicals, optionally interrupted by or substituted with at least        one group chosen from C₁-C₃₀ alcohol ester, amine, carboxyl,        alkoxysilane, C₆-C₃₀ aryl, hydroxyl, and carbonyl groups, and    -   s=0 or 1.

In a further exemplary embodiment, the at least one alkoxysilanecomprising at least one solubilizing functional group is chosen fromcompounds of formula (XV):

wherein, in formula (XV), the R radicals, which may be identical ordifferent, are chosen from C₁-C₆ alkyl radicals and n is an integerranging from 1 to 6, for example, from 2 to 4.

The alkoxysilanes useful in the present disclosure can be chosen fromalkoxysilanes comprising a silicon atom of formula R_((4-n))SiX_(n),wherein X is a hydrolysable group such as methoxy, ethoxy or2-methoxyethoxy, R is a monovalent organic radical which contains 1 to12 carbon atoms and may contain groups such as mercapto, epoxy, acrylyl,methacrylyl, amino or urea, and n is an integer from 1 to 4, andaccording to at least one embodiment is 3. Exemplary alkoxysilanesinclude, but are not limited to, 3-mercaptopropyltriethoxysilane andaminoalkyltrialkoxysilanes such as 3-aminopropyltriethoxysilane, asdescribed in French Patent Application No. FR2789896, incorporated byreference herein.

Other useful alkoxysilanes are cited, for example, in EP1216022,incorporated by reference herein, which describes alkoxysilanescomprising at least one hydrocarbon chain containing a non-basicsolubilizing chemical function. In this respect, non-limiting mentionmay be made of the HCl-neutralized sodiumN-[(3-trimethoxysilyl)propyl]ethylenediaminetriacetate supplied byGELEST.

According to at least one embodiment, the alkoxysilanes may comprise atleast one hydrocarbon chain containing fluorine atoms. Possible examplesinclude but are not limited to the 3,3,3-trifluoropropyltriethoxysilaneor tridecafluorooctyltriethoxysilane compounds described in EP1510197,incorporated by reference herein.

In another embodiment, the useful alkoxysilanes may be alkoxysilaneswhich carry a group having a cosmetic functional group, such as aromaticnitro dyes or anthraquinone, napthoquinone, benzoquinone, azo, xanthene,triarylmethane, azine, indoaniline, indophenolic or indoamine dyes;groups having a reductive effect, such as thiol groups, sulphinic acidor sulphinic salt, it being possible for these alkoxysilanes to carry asolubilizing non-hydrolysable group such as amino groups, carboxylicacids, sulphonic acids, sulphates, quaternary ammoniums, polyalcohols,polyether and phosphates. One possible example includesaminopropyl-N-(4,2-dinitrophenyl)aminopropyldiethoxysilane. Exemplarycompounds of this type are described, for example, in EP1216023,incorporated by reference herein.

The alkoxysilanes of the present disclosure may be amino arylalkoxysilanes. Non-limiting examples include the following, all of whichare provided by GELEST:

3-(m-aminophenoxy)propyltrimethoxysilane, of the formula:

p-aminophenyltrimethoxysilane, of formula:

and

N-(2-aminoethylaminomethyl)phenethyltrimethoxysilane, of the formula:

The alkoxysilanes of the present disclosure may be silanes having analdehyde or acetal functional group.

The alkoxysilanes may also be silanes containing non-primary amines,such as the bis[3-(triethoxysilyl)propyl]amine of the formula(CH₃CH₂O)₃—Si(CH₂)₃NH(CH₂)₃Si(OCH₂CH₃)₃ provided by Fluorochem, thebis[trimethoxysilylpropyl]amine of the formula(CH₃O)₃—Si(CH₂)₃NH(CH₂)₃Si(OCH₃)₃ provided by Gelest, thebis[methyldiethoxysilylpropyl]amine of the formula(CH₃CH₂O)₂CH₃Si(CH₂)₃NH(CH₂)₃SiCH₃(OCH₂CH₃)₂ provided by Gelest and thebis[3-trimethoxysilylpropyl]ethylenediamine of formula(CH₃O)₃Si(CH₂)₃NH(CH)₂NH(CH₂)₃Si(OCH₃)₃ provided by Gelest.

In other exemplary embodiments, the silane compound may be chosen fromoctadecyltrichlorosilane and derivatives thereof.

In other various exemplary embodiments, the at least one silane compoundmay be chosen from those described in US 20080184495, incorporated byreference herein, including, for example, alkoxysilane compoundscomprising at least one —Si—OR portion, wherein R is an alkyl groupcomprising from 1 to 6 carbon atoms.

By way of example, the at least one silane may be chosen fromorganosiloxanes comprising at least 2 alkoxysilane end groups and/ortrialkoxysilane end groups.

In at least one exemplary embodiment, the at least one silane may bechosen from Bis-PEG-18 Methyl Ether Dimethyl Silane, sold by DowCorning.

In another exemplary embodiment, the at least one silane is atrialkoxysilane comprising an amino substituent.

In particularly preferred exemplary embodiments, the at least one silaneis γ-aminopropyltriethoxysilane, also known as3-aminopropyltriethoxysilane, commercially available under thetradename, KBE-903™, from Shin-Etsu, and also under the tradename,Silsoft® A-1100, from Momentive Performance Materials.

In various embodiments, the at least one silane may be present in anamount ranging from about 0.1% to about 40% by weight, such as fromabout 0.1% to about 30% by weight, from about 0.5% to about 30% byweight, from about 0.5% to about 25% by weight, or from about 1% toabout 20% by weight, based on the total weight of the composition.

Activators

According to various embodiments of the disclosure, one or more phasesof the compositions described herein may comprise at least oneactivator. Without wishing to be bound by theory, it is believed thatactivators increase the lightening effect of other components, therebyproviding compositions having superior lightening power in less time,and therefore minimizing the damage to the hair and/or skin. This islikewise believed to be even more useful when, as in various embodimentsherein, successive chemical treatments are applied to the hair in ashort period of time.

Exemplary activators that may be used according to various embodimentsof the disclosure include, but are not limited to, cationic pyridiniumderivatives, such as those disclosed in WO2010054981; cationicacylpyridinium derivatives, such as those disclosed in US2011232669,US2011047712, and US2011146006; saccharin derivatives, such as thosedisclosed in DE102010043497; cationic phthalamide derivatives, such asthose disclosed in WO2011079974; cationic 3,4-dihydroisoquinoliniumderivatives, such as those disclosed in US2011146005; sulfoniminederivatives, such as those disclosed in WO2011064007;1,2-dihydropyrimidinium derivatives, such as those disclosed inDE102006031470; diacylated 2,5-diketopiperizine derivatives, such asthose disclosed in U.S. Pat. No. 3,775,332;N-acylated-2,4,6,8-tetraazabicyclo-(3,3,1)-nonan-3,7-diones, such asthose disclosed in U.S. Pat. No. 3,825,543; and acylated glycolurilderivatives, such as those disclosed in U.S. Pat. No. 3,715,184, all ofwhich are incorporated by reference herein.

Other exemplary activators that may be used in the composition include,but are not limited to, aliphatic and carboxylic activators. In variousembodiments, activators contain a hydroxyl group, a carboxylic acid, asulfuric acid monoester, a phosphoric acid monoester, and/or aphysiologically acceptable salt thereof.

By way of example, activators may be chosen from compounds of thegeneral formula (XVI):

wherein, in formula (XVI):

-   -   Y is a carbonyl group, a direct bond or methylene group;    -   R1 is hydrogen, a C₁-C₄ alkyl group, a physiologically        acceptable cation or an SO₃ ⁻ or a PO₃ ²⁻ group;    -   R2 is an amino, a methylamino, a dimethylamino, a        trimethylammonio group, phenyl, benzyl, phenoxymethyl,        1-naphthyl, 2-naphthyl, 2-, 3-, 4-toluoyl, or an        R4-O—(CH₂CH₂O)_(n) group, wherein R4 is a C₆-C₂₀ alkyl group and        n is a number 15 or greater; and    -   R3 is hydrogen or an optionally branched C₁-C₆ alkyl group;        provided that:    -   if Y is a carbonyl group, R1 is hydrogen, a C₁-C₄ alkyl group or        a physiologically acceptable cation, R2 is an amino, a        methylamino, a dimethylamino or a trimethylammonio group, and R3        is hydrogen or an optionally branched C₁-C₆ alkyl group;    -   if Y is a direct bond, R1 is hydrogen, R2 is phenyl, benzyl,        phenoxymethyl, 1-naphthyl, 2-naphthyl, 2-, 3- or 4-toluoyl, and        R3 is hydrogen or an optionally branched C₁-C₆ alkyl group; or    -   if Y is a methylene group, R1 is an SO₃ ⁻ or a PO₃ ²⁻ group, R2        is an R4-O—(CH₂CH₂O)_(n) group, wherein R4 is a C₆-C₂₀ alkyl        group and n is a number greater than 15, and R3 is hydrogen.

Non-limiting examples of activators useful according to embodiments ofthe disclosure include activators such as glycine, N-methyl glycine,N,N-dimethyl glycine, alanine, N-methyl alanine, N,N-dimethyl alanine,leucine, N-methyl leucine, N,N-dimethyl leucine, isoleucine, N-methylisoleucine, N,N-dimethyl isoleucine, and physiologically acceptablesalts thereof.

In various embodiments, the activator may be chosen from glycine,aromatic alcohols, and physiologically acceptable salts thereof.Exemplary and non-limiting aromatic alcohols may include benzyl alcohol,2-phenylethyl alcohol, 1-phenylethyl alcohol, 2-phenoxyethanol,1-hydroxymethylnaphthalene and/or 2-hydroxymethylnaphthalene.

In further exemplary embodiments, activators may be chosen fromphysiologically acceptable salts of an alkyl ether sulfate having thegeneral formula (XVII):

R4-O(CH₂CH₂O)_(m)SO₃Y

wherein, in formula (XVII), R4 is a C₆-C₂₀ alkyl group; m is a numberfrom 15 or greater; and Y is an alkali metal and/or alkaline earthmetal, ammonium, alkylammonium or alkanolammonium.

In at least one exemplary embodiment, the activator may be SodiumCoceth-30 Sulfate and is distributed by Cognis as a 31-33 wt % aqueoussolution under the trade name Disponil® FES 77.

In embodiments where the activator contains a structural unit whichallows a plurality of spatial arrangements, such as substituted doublebonds or centers of asymmetry, it is understood that all possiblestereoisomers are included. It may optionally, however, also be possibleto use either just one stereoisomer, or a mixture of two or morestereoisomers.

In various embodiments, the at least one activator may be present in anamount ranging from about 0.01% to about 15% by weight, such as fromabout 0.1% to about 12% by weight, from about 0.5% to about 10% byweight, or from about 1% to about 5% by weight, based on the totalweight of the composition.

Lift-Enhancing Agents

In addition to the lift-enhancing agents described above, exemplarylift-enhancing agents that may be used as auxiliary ingredients include,but are not limited to, metal catalysts, such as, for example, magnesiumhydroxide and magnesium carbonate.

Other Ingredients

The compositions of the present invention can also comprise any additivetypically used in cosmetic or hair treatment compositions. Suchadditives can be present in the pre-alkalizing composition, thecolor-altering composition, and/or the post-treatment composition.Exemplary additives may include waxes, organogelators, thickening agentssuch as organophilic clays, dispersants, oils, preserving agents,fragrances, fillers, neutralizing agents, hydroxy acids, UV filters,acidifying agents, buffering agents, conditioning agents, surfactants,antioxidants, fragrances, vitamins, and provitamins.

The composition according to the invention may comprise one or morenatural dyes. Non-limiting examples of natural dyes that may be choseninclude lawsone, juglone, alizarin, purpurin, carminic acid, kermesicacid, laccaic acid, purpurogallin, anthragallol, protocatechaldehyde,indigo, isatin, curcumin, spinulosin, chlorophylls, chlorophyllines,orceins, haematin, haematoxylin, brazilin, brazileine, safflower dyes(for instance carthamine), flavonoids (with, for example, morin,apigenidin and sandalwood), anthocyans (of the apigeninidin type),carotenoids, tannins, sorghum and cochineal carmine, or mixturesthereof.

Extracts or decoctions containing these natural dyes, and especiallyhenna-based extracts, may also be used.

For example, the natural dyes are chosen from lawsone, juglone,alizarin, purpurin, carminic acid, kermesic acid, laccaic acid,purpurogallin, protocatechaldehyde, indigo, isatin, curcumin,spinulosin, apigenidin, chlorophylline, sorghum, orceins, cochinealcarmine, haematin, haematoxylin, brazilin and brazileine, and mixturesthereof.

These dyes may optionally be used in the presence of mordants (forexample zinc, manganese, aluminium, iron, etc. salts).

The natural dyes, when they are present, may, for example, representfrom about 0.001% to about 10% by weight, such as from about 0.01% toabout 8% by weight, or from about 0.1% to about 5% by weight, relativeto the weight of the composition.

Needless to say, a person skilled in the art will take care to selectthe optional additional compound(s) mentioned above such that theadvantageous properties intrinsically associated with the methods andcompositions of the present invention disclosed herein are not, or arenot substantially, adversely affected by the envisaged addition(s).

Heat Treatment

As an additional, optional step, for example during or after one or moreof steps (a), (c), or (d), above, such as subsequent to the applicationof the color-altering composition, the hair may be treated with heat.The heat treatment may optionally be effectuated by any means known,such as, for example, by use of a hair dryer/hood, hot/flat iron,exposure to ultraviolet (UV) light, etc.

The step of exposing the hair to heat may last for any amount of time,such as about 0.1 second to about 1 hour, for example from about 5minutes to about 50 minutes, about 10 to about 45 minutes, such as about30 minutes. In various embodiments, the heat treatment may be at atemperature of at least about 50° C., such as at least about 75° C., atleast about 100° C., or at least 150° C. By way of example, thetemperature may range from about 50° C. to about 250° C.

The heat treatment may optionally be accompanied by a smoothing step.

Application

The compositions according to various embodiments of the disclosure maybe in any form known to those of skill in the art, and may be applied tothe hair by any method known. By way of example only, the compositionsmay be provided in a multiple-agent container, e.g. as a foam.

In at least one exemplary embodiment, methods for altering the color ofhair comprise discharging a composition as described herein in the formof a foam from a squeeze container, aerosol container, and the like, forexample as described in WO2008136433, GB2219352A, JP5155742A2, andUS20030084517, all of which are incorporated by reference herein.

According to various embodiments disclosed herein, the color-alteringcomposition is applied to the pre-alkalized hair without the use of adeveloper. Conventional dyeing processes often require the pre-mixing ofthe color-altering composition with a developer, such as hydrogenperoxide, followed by the application of the mixture to the hair fibers.These processes may be messy and/or time-consuming. In contrast, themethods disclosed herein may allow the hair color to be developed insitu, e.g., directly on the hair fibers without the need for adeveloper.

Unless expressly indicated otherwise, all numeric quantities are to beunderstood as being modified in all instances by the term “about,”whether or not so stated, meaning within 10% of the indicated number.

As used herein, the expressions “substantially free” and “substantiallyno” are to be understood as meaning less than about 0.05 wt % of theindicated compound, relative to the total weight of the composition. Forinstance, a color-altering composition comprising substantially nochemical oxidizing agents is understood to mean a composition comprisingless than about 0.05 wt % of chemical oxidizing agents, relative to thetotal weight of the color-altering composition. By way of non-limitingexample, the color-altering composition may comprise less than about0.04 wt %, such as less than about 0.03 wt %, less than about 0.02 wt %,or less than about 0.01 wt % of chemical oxidizing agents, relative tothe total weight of the composition.

As used herein, the expression “at least one” means one or more and thusincludes individual components as well as mixtures/combinations. As usedherein, the terms “a,” “an,” and “the” are meant to signify “at leastone,” unless expressly otherwise indicated. Thus, the phrase “a directdye” means one or more direct dyes.

As used herein, the term “hair” is meant to include keratinous fibers.As used, the term “hair” may include “living” hair, i.e. on a livingbody, or may be “non-living” i.e. in a wig, hairpiece or otheraggregation of non-living fibers, such as though used in textiles andfabrics. Mammalian hair, e.g. human hair, is preferred in variousembodiments. However wool, fur and other melanin-containing fibers aresuitable for use in the methods and with the compositions describedherein.

The term “anhydrous” as used herein is intended to mean that thecomposition is either completely free of unbound water or containssubstantially no unbound water, such as, for example, no more than about1% by weight, such as no more than about 0.5% by weight, based on theweight of each composition.

As used herein, the phrase “salts and derivatives thereof” is intendedto mean all salts and derivatives comprising the same functionalstructure as the compound they are referring to, and that have similarproperties.

As used herein, the terms “pre-alkalizing” and “pre-alkalized” mean thatthe hair has a higher pH than when it has not been subjected to chemicaltreatment, as described herein. In certain embodiments, the pH of thepre-alkalized hair may be greater than about 7, for example, rangingfrom about 7 to about 14, from about 7.5 to about 14, or from about 8 toabout 14.

As used herein, the phrase “color-altering composition” means acomposition that brings about a change in hair color, including, forexample, bleaching, lightening, dyeing, etc.

As used herein, the phrase “minimizing damage” to the hair and/or skinis intended to mean that the breakage of the hair has been reduced oreliminated.

As used herein, the term “ready-to-use composition” means a compositionintended to be applied in unmodified form to the keratin fibers, i.e. itmay be stored in unmodified form before use or may result from theextemporaneous mixing of two or more compositions.

As used herein, the expression “chemically altering” means contactingthe hair with at least one composition containing at least one chemicalingredient that changes or contributes to changing the shape and/or thecolor of the hair, to any degree.

As used herein, the term “applying” a composition to the hair or“treating” the hair with a composition is intended to mean contactingthe hair with at least one of the compositions of the invention, in anymanner.

As used herein, the terms “straightening” or “straighten” or “relaxing”or “relax” the hair mean to remove the curl from the hair or reduce thedegree of curl of the hair. It also means changing the shape of hair orthe degree of curl in the hair to make the hair more straight. It canalso mean removing or reducing the frizziness of the hair.

As used herein, “cosmetically acceptable” means that the item inquestion is compatible with any human keratin material and in particularhuman keratinous fibers, such as human hair.

As used herein, “cosmetically acceptable carrier” means a carrier thatis compatible with any human keratin material and in particular humankeratinous fibers, such as human hair.

As used herein, “recently contacted” means that the time period betweencontacting the hair with a chemical composition according to variousmethods is not more than about twenty four hours.

As used herein, “natural hair color” refers to the color of hairresulting from the melanin pigments present in the hair.

As used herein, “conditioning” means imparting to at least onekeratinous fiber at least one property chosen from combability,manageability, moisture-retentivity, luster, shine, and softness. Incase of combing, the level of conditioning is evaluated by measuring,and comparing, the ease of combability of the treated hair and of theuntreated hair in terms of combing work (gm-in).

As used herein, “formed from,” means obtained from chemical reaction of,wherein “chemical reaction,” includes spontaneous chemical reactions andinduced chemical reactions. As used herein, the phrase “formed from”, isopen ended and does not limit the components of the composition to thoselisted.

As used herein, the term “rheology-modifying agent” or “rheologymodifier” means any compound capable of giving a viscosity to acomposition such that, once it is applied onto hair, this compositiondoes not run, and remains perfectly localized at the point ofapplication.

As used herein, the methods and compositions disclosed may be used onthe hair that has not been artificially dyed or pigmented.

As used herein, the methods and compositions disclosed may be also usedon the hair that has been artificially dyed or pigmented.

It is to be understood that the foregoing describes various exemplaryembodiments of the invention, but that modifications may be made thereinwithout departing from the spirit or scope of the invention as set forthin the claims.

Example

Color Altering Composition % Concentration INCI Name Commercial Nameactivity wt (%) Laureth-12 Alkonat L 120 100 3 (Oxiteno) Oleth-30Genapul U 300 F 100 2 (Clariant) Sodium Cetearyl Sulfate Lanette eGranules 96 1.5 (Cognis) Cetearyl Alcohol N/A 2 Sodium Sulfate N/A 2Laureth-2 Arylpon F 100 8 (Cognis) PEG-4 Rapeseedamide Amidet N 92.305 4(Kao) Trideceth-2 Amidet A15/Lao 15 100 4 (Kao) Glycerin Glycerine 4833100 3 (Oleon) Polyquaternium-6 Merquat 100 polymer 40 2 (Nalco)3-Nitro-p-Hydroxyethylaminophenol NHEAP PREMIUM GRADE 100 0.3 (Artec)4-Amino-3-Nitrophenol 4-AMINO-3-NITRO PHENOL (IMEXINE 100 0.4 FN)(Dragon Chemical) HC Yellow No. 9 IMEXINE FAD 100 0.2 (Chimex) HC RedNo. 3 HC Red 3 100 0.6 (Lowenstein) Cetyl HydroxyethylcelluloseNatrolsol Plus 330 C S 100 0.4 (Ashland) MEA Monoethanolamine pHadjuster (Oxiteno) Deionized water N/A 100 QS

Comparative Procedures A1 and A2

Virgin hair samples comprising 90% gray fibers were dyed with thecolor-altering composition, in the absence of a developer. Thecolor-altering composition was left in contact with the hair fibers for20 minutes and then washed from the hair using a standard neutralizingshampoo. In procedure A1, the color-altering composition did notcomprise glycine. In procedure A2, the color-altering compositioncomprised 5 wt % glycine (Ajinomoto).

Comparative Procedures B1 and B2

Virgin hair samples comprising 90% gray fibers were dyed with a 1:1mixture of the color-altering composition and a peroxide developercomprising 6 wt % of a 50/50 hydrogen peroxide solution. The mixture wasleft in contact with the hair fibers for 20 minutes and then washed fromthe hair using a standard neutralizing shampoo. In procedure B1, thecolor-altering composition did not comprise glycine. In procedure B2,the color-altering composition comprised 5 wt % glycine (Ajinomoto).

Inventive Procedures C1 and C2

Relaxed (pre-alkalized, pH=7.7) hair samples comprising 90% gray fiberswere dyed with the color-altering composition, in the absence of adeveloper. The color-altering composition was left in contact with thehair fibers for 20 minutes and then washed from the hair using astandard neutralizing shampoo. In procedure C1, the color-alteringcomposition did not comprise glycine. In procedure C2, thecolor-altering composition comprised 5 wt % glycine (Ajinomoto).

Comparative Procedures D1 and D2

Relaxed (pre-alkalized, pH=7.7) hair samples comprising 90% gray fiberswere dyed with a 1:1 mixture of the color-altering composition andperoxide developer. The mixture was left in contact with the hair fibersfor 20 minutes and then washed from the hair using a standardneutralizing shampoo. In procedure D1, the color-altering compositiondid not comprise glycine. In procedure D2, the color-alteringcomposition comprised 5 wt % glycine (Ajinomoto).

Evaluation

A colorimetric evaluation of the hair fibers was performed with aDataColor SF600X spectrocolorimeter using the CIELab system. Accordingto this system, L indicates the lightness of the hair, where a moreintense hair color is indicated by a lower L value. dE indicates thedegree of lightening of the hair, representing the difference in colorbetween the treated and untreated fibers. A more intense hair lighteningis indicated by a higher dE value. dE is calculated as follows:

dE=√{square root over ((L−L _(o))²+(a−a _(o))²+(b−b _(o))²)}{square rootover ((L−L _(o))²+(a−a _(o))²+(b−b _(o))²)}{square root over ((L−L_(o))²+(a−a _(o))²+(b−b _(o))²)}

where L, a, and b represent the values measured for untreated fibers andL₀, a₀, and b₀ represent the values measured for treated fibers. Thefollowing results were obtained.

Virgin Hair Samples L A b dE Hair pH Control - 90% gray Virgin 60.090.53 13.61 — 5.3 A1 (no developer, no glycine) 32.26 26.11 18.41 38.16.1 A2 (no developer, glycine) 37.25 25.45 21.39 34.69 6.5 B1 (1:1peroxide developer, 35.55 26.25 20.47 36.2 6.1 no glycine) B2 (1:1peroxide developer, 34.21 23.49 19.36 35.07 6 glycine)

Relaxed Hair Samples L A b dE Hair pH Control - 90% gray Relaxed 56.230.63 22.85 — 7.7 C1 (no developer, no glycine) 22.18 19.92 9.18 41.457.3 C2 (no developer, glycine) 24.7 22.12 11.46 39.82 6.6 D1 (1:1peroxide developer, 27.07 24.6 14.88 38.58 5.9 no glycine) D2 (1:1peroxide developer, 26.59 25.83 14.96 39.7 6.2 glycine)

Discussion

It was noted that the relaxed hair samples exhibited an alkaline pH(7.7) before dyeing, whereas the virgin hair samples exhibited an acidicpH (5.3) before dyeing. Furthermore, it was noted that the relaxed hairsamples were generally more intensely dyed (lower L value) and moreeffectively lightened (higher dE value), as compared to the virgin hairsamples. Without wishing to be bound by theory, it is believed that thepre-alkalizing step opens the hair cuticle, thereby rendering it moresusceptible to penetration by the color-altering composition.

Traditional hair dyeing methods employing peroxide developers (D1 andD2) generally dye and/or lighten the hair effectively, but can be messy,time-consuming, and/or damaging to the hair. It would therefore bedesirable to develop dyeing methods not employing such developers.According to the inventive methods disclosed herein (C1 and C2), the useof peroxide developers and the drawbacks associated therewith can beavoided while also providing improved color intensity and lightening.Hair fibers dyed according to the inventive methods (C1 and C2) are moreintensely dyed (lower L value) and more effectively lightened (higher dEvalue) as compared to fibers dyed according to methods employingperoxide developers (D1 and D2).

It is to be understood that the foregoing describes various exemplaryembodiments of the invention, but that modifications may be made thereinwithout departing from the spirit or scope of the invention as set forthin the claims.

1. A method of altering the appearance of hair, said method comprising:(a) applying onto the hair, a pre-alkalizing composition having a pH offrom about 8 to about 14 to form pre-alkalized hair; (b) optionally,rinsing the hair; (c) optionally shampooing and rinsing the hair; (d)applying a color-altering composition onto the pre-alkalized hair,wherein the color-altering composition comprises, in a cosmeticallyacceptable carrier: (i) at least one direct dye; and (ii) optionally atleast one oxidative dye precursor; and wherein the pH of thecolor-altering composition ranges from about 1 to about 7; (e) leavingthe color-altering composition on the hair for a time period sufficientto achieve a desired level of color lift; and (f) optionally, rinsingthe hair; wherein the color-altering composition does not comprise achemical oxidizing agent; and wherein the color-altering composition isapplied onto the pre-alkalized hair within about 24 hours after thepre-alkalizing step.
 2. The method according to claim 1, wherein thepre-alkalizing composition contains at least one auxiliary ingredientchosen from rheology-modifying agents, chelants, fatty substances,surfactants, substantive polymers, ceramides, alkoxyaminosilicones,fragrances, and silanes.
 3. The method according to claim 1, wherein thecolor-altering composition is a ready-to-use composition.
 4. The methodaccording to claim 1, wherein the at least one direct dye is chosen fromazo direct dyes, methine direct dyes, carbonyl direct dyes, azine directdyes, nitro(hetero)aryl direct dyes, tri(hetero)arylmethane direct dyes,addition salts thereof, and mixtures thereof.
 5. The method according toclaim 1, wherein the at least one direct dye is present in an amountranging from about 0.001% to about 20% by weight, relative to the totalweight of the color-altering composition.
 6. The method according toclaim 1, wherein the at least one oxidative dye precursor is chosen fromortho aminophenols, para aminophenols, ortho phenylenediamines, paraphenylenediamines, double bases, heterocyclic bases, acid addition saltsthereof, and mixtures thereof.
 7. The method according to claim 1,wherein the color-altering composition further comprises at least oneauxiliary ingredient chosen from rheology-modifying agents, activators,chelants, fatty substances, ceramides, alkoxyaminosilicones, silanes,and lift-enhancing agents chosen from nitrogen-containing compounds andmetal catalyst compounds.
 8. The method according to claim 1, whereinthe color-altering composition further comprises at least one fattysubstance.
 9. The method according to claim 1, wherein thecolor-altering composition is applied onto the hair within a time periodof less than 12 hours after the pre-alkalizing composition is appliedonto the hair.
 10. The method according to claim 1, wherein thecolor-altering composition is left on the hair for a time period rangingfrom about 3 to about 60 minutes.
 11. The method according to claim 1,further comprising applying a post-treatment composition onto the hair.12. The method according to claim 11, wherein the post-treatmentcomposition contains at least one auxiliary ingredient chosen fromrheology-modifying agents, chelants, fatty substances, ceramides,alkoxyaminosilicones, and silanes.
 13. The method according to claim 1,further comprising applying heat to the hair after the application ofthe color-altering composition onto the hair.
 14. A method of alteringthe appearance of hair, said method comprising: (a) applying onto thehair, a pre-alkalizing composition having a pH of from about 8 to about14 to form pre-alkalized hair; (b) optionally, rinsing the hair; (c)optionally shampooing and rinsing the hair; (d) applying acolor-altering composition onto the pre-alkalized hair, wherein thecolor-altering composition comprises, in a cosmetically acceptablecarrier: (i) at least one direct dye; (ii) at least one additionalingredient chosen from rheology-modifying agents, activators, chelants,fatty substances, lift-enhancing agents, de-dusting agents,alkoxyaminosilicones, silane compounds, and ceramide compounds; and(iii) optionally at least one oxidative dye precursor; and wherein thepH of the color-altering composition ranges from about 1 to about 7; (e)leaving the color-altering composition on the hair for a time periodsufficient to achieve a desired level of color lift; and (f) optionally,rinsing the hair; wherein the color-altering composition does notcomprise a chemical oxidizing agent; and wherein the color-alteringcomposition is applied onto the pre-alkalized hair within about 24 hoursafter the pre-alkalizing step.
 15. The method according to claim 14,wherein the at least one direct dye is present in an amount ranging fromabout 0.001% to about 20% by weight, relative to the total weight of thecolor-altering composition.
 16. The method according to claim 14,wherein the color-altering composition is applied onto the hair within atime period of less than 12 hours after the pre-alkalizing compositionis applied onto the hair.
 17. The method according to claim 14, whereinthe color-altering composition is left on the hair for a time periodranging from about 3 to about 60 minutes.
 18. The method according toclaim 14, further comprising applying a post-treatment composition ontothe hair.
 19. The method according to claim 18, wherein thepost-treatment composition contains at least one auxiliary ingredientchosen from rheology-modifying agents, chelants, fatty substances,ceramides, alkoxyaminosilicones, and silanes.
 20. The method accordingto claim 14, further comprising applying heat to the hair after theapplication of the color-altering composition onto the hair.